Self-reactive/curable water-based solid adhesive and method of bonding with the self-reactive/curable water-based solid adhesive

ABSTRACT

Self-curable water-based solid adhesives of this invention include the following components (A), (B), (C), and (D):  
     (A) an anionic-group-containing polymer terminally having an alkoxysilyl group, the polymer being a reaction product of a compound (A1) containing no anionic group and having plural isocyanate-reactive groups, a compound (A2) having an anionic group and plural isocyanate-reactive groups, a polyisocyanate compound (A3), and an alkoxysilane compound (A4) containing an isocyanate-reactive group;  
     (B) a basic compound;  
     (C) water; and  
     (D) a gelling agent.  
     The self-curable water-based solid adhesives of the present invention can be applied with good workability, have good fitting after attachment, have good adhesion to plastics, metals and glass and exhibit excellent heat resistance and water resistance after curing. They are highly safe to humans and the environment. They also have excellent shape retention and slidability and can be easily applied. In addition, they can bond adherends by contact bonding despite that they are water-based solid adhesives. Accordingly, the self-curable water-based solid adhesives of this invention are very useful as stick adhesives.

TECHNICAL FIELD

[0001] The present invention relates to a water-based solid adhesive anda bonding method using the water-based solid adhesive. Morespecifically, it relates to a water-based solid adhesive exhibiting goodadhesion to various adherends and having excellent water resistance andheat resistance, and to a bonding method using the water-based solidadhesive.

BACKGROUND ART

[0002] Stick adhesives mainly comprising a water-soluble polymer, agelling agent, and water can be easily applied, have good fitting afterattachment and are therefore widely used as water-based solid adhesives.However, the fact is that these stick adhesives are used in bonding ofpaper, since the water-soluble polymer itself exhibits adhesion toadherends in a very limited range. Demands have therefore been made ondevelopment of stick adhesives that can adhere to, for example, wood,plastics, and metals. As a possible solution to this problem, a stickadhesive comprising a water-based polyurethane dispersion has beenproposed as described in Japanese Patent No. 2836957. However, thisstick adhesive exhibits insufficient adhesion to metals and glass,although it has improved adhesion to plastics. The stick adhesive alsohas insufficient heat resistance and water resistance, since thewater-based polyurethane dispersion is a non-reactive polymer and issubstantially linear polymer. If an amine chain extender is added tosuch a water-based polyurethane dispersion for imparting heat resistanceand water resistance, the resulting water-based polyurethane dispersionhas a high molecular weight of several hundred thousands, constitutes anemulsion having a relatively large particle size and cannot besignificantly molded into a stick adhesive.

DISCLOSURE OF INVENTION

[0003] Accordingly, an object of the present invention is to provide awater-based solid adhesive that can be applied with good workability,has good fitting after attachment, exhibits good adhesion to plastics,metals and glass and has excellent heat resistance and water resistanceafter curing.

[0004] Another object of the present invention is to provide awater-based solid adhesive that can perform contact bonding or exhibitsfurther improved initial adhesion, and a bonding method using thewater-based solid adhesive.

[0005] After intensive investigations to achieve the above objects, thepresent inventors have found that, when a specific polymer which has analkoxysilyl group at its end and is cured as a result of a condensationreaction with a silanol group is used as an adhesive component of awater-based solid adhesive, the resulting water-based solid adhesive isself-curable, can be applied with good workability, has good fittingafter attachment, can exhibit good adhesion or adhesiveness to plastics,metals and glass, has excellent heat resistance and water resistanceafter curing and can bond adherends by contact bonding or with furtherhigher initial adhesive strength. The present invention has beenaccomplished based on these findings.

[0006] Specifically, the present invention provides, in an aspect, aself-curable water-based solid adhesive containing the followingcomponents (A), (B), (C), and (D):

[0007] (A) an anionic-group-containing polymer terminally having analkoxysilyl group, the polymer being a reaction product of a compound(A1) containing no-anionic group and having plural isocyanate-reactivegroups, a compound (A2) having an anionic group and pluralisocyanate-reactive groups, a polyisocyanate compound (A3), and analkoxysilane compound (A4) containing an isocyanate-reactive group;

[0008] (B) a basic compound;

[0009] (C) water; and

[0010] (D) a gelling agent.

[0011] The self-curable water-based solid adhesive of the presentinvention may be a gelled product of a water-based resin composition byaction of the gelling agent (D), which water-based resin compositioncontains the anionic-group-containing polymer (A) terminally having analkoxysilyl group, the basic compound (B), and water (C). Preferably,the anionic group of the anionic-group-containing polymer (A) terminallyhaving an alkoxysilyl group is neutralized by the basic compound (B),and the alkoxysilyl group at the end of the anionic-group-containingpolymer (A) is hydrolyzed by the water (C) in the water-based resincomposition gelled by the gelling agent (D).

[0012] The anionic-group-containing polymer (A) terminally having analkoxysilyl group is preferably an anionic-group-containing polymerhaving an alkoxysilylated end and being a reaction product of ananionic-group-containing polymer and the alkoxysilane compound (A4)containing an isocyanate-reactive group, the anionic-group-containingpolymer being a reaction product among the compound (A1) containing noanionic group and having plural isocyanate-reactive groups, the compound(A2) having an anionic group and plural isocyanate-reactive groups, andthe polyisocyanate compound (A3).

[0013] The compound (A1) containing no anionic group and having pluralisocyanate-reactive groups may contain a compound (A1-1) having anumber-average molecular weight of equal to or more than 500, containingno anionic group and having plural isocyanate-reactive groups, and acompound (A1-2) having a number-average molecular weight of less than500, containing no anionic group and having plural isocyanate-reactivegroups.

[0014] The anionic group for use in the present invention is preferablya carboxyl group. The compound (A2) having an anionic group and pluralisocyanate-reactive groups is preferably a dimethylolalkanoic acid.

[0015] The isocyanate-reactive group of the alkoxysilane compound (A4)is preferably a primary amino group, a secondary amino group, or amercapto group.

[0016] The alkoxysilane compound (A4) can be an alkoxysilane compoundhaving a secondary amino group and being a reaction product of analkoxysilane compound having at least a primary amino group, preferablyan alkoxysilane group having primary and secondary amino groups, with anunsaturated carboxylic ester (A5).

[0017] The self-curable water-based solid adhesive of the presentinvention preferably further contains a polyoxyalkylene compound (E)having an unsaturated-bond-containing organic group and at least anoxyethylene unit. The polyoxyalkylene compound (E) is preferably apolyoxyalkylene compound having an unsaturated-bond-containing group atits end corresponding to a polyoxyalkylene glycol having at least apolyoxyethylene unit except with one of aryl groups, cycloalkenylgroups, cycloalkadienyl groups, and vinyl group introduced into at leastone of ends of the polyoxyalkylene glycol.

[0018] The self-curable water-based solid adhesive of the presentinvention preferably further contains a curing accelerator (F)represented by following Formula (1):

[0019] wherein M is one of tin atom, titanium atom, zirconium atom andbismuth atom; R¹ and R² are the same or different and are each ahydrocarbon group; R³ and R⁴ are the same or different and are each ahydrogen atom or a hydrocarbon group; R⁵ and R⁶ are the same ordifferent and are each a hydrogen atom or a hydrocarbon group; p is aninteger equal to or more than 1; and q is an integer from 1 to 3.

[0020] The present invention also provides, in another aspect, a bondingmethod including the step of performing contact bonding using theself-curable water-based solid adhesive.

[0021] In yet another aspect, the present invention provides ananionic-group-containing polymer represented by following Formula (2)terminally having an alkoxysilyl group, a salt thereof, or a hydrolyzedpolymer being derived from the polymer or the salt thereof andcontaining a hydrolyzed alkoxysilyl group:

WNH—CO—X)_(n)   (2)

[0022] wherein W is a residue corresponding to a skeleton of ananionic-group-containing polymer; the nitrogen atom combined with W is anitrogen atom derived from an isocyanate group at the end of theanionic-group-containing polymer; W has a structural unit represented byfollowing Formula (2a):

NH—CO—V—Y—V—CO—NH-Z  (2a)

[0023] wherein Y is one of a residue derived from a compound (A1)containing no anionic group and having plural isocyanate-reactive groupsand a residue derived from a compound (A2) having an anionic group andplural isocyanate-reactive groups; V combined with Y is a group derivedfrom one of the isocyanate-reactive groups of the compound (A1) and thecompound (A2), wherein both the residue derived from the compound (A1)and the residue derived from the compound (A2) as Y are contained in thepolymer; Z is a residue derived from a polyisocyanate compound (A3),wherein a nitrogen atom combined with Z and a nitrogen atom on theopposite side to Z are nitrogen atoms derived from isocyanate groups ofthe polyisocyanate compound (A3);

[0024] X is an alkoxysilyl-containing group represented by any one offollowing Formulae (2b), (2c), and (2d):

[0025] wherein R⁷ and R⁸ are the same or different and are each an alkylgroup; R⁹ is an alkylene group; R¹⁰ and R¹² are the same or differentand are each a hydrogen atom or an alkyl group; R^(11a) is a hydrogenatom or an alkyl group; R¹³ is an alkyl group, an aryl group or acycloalkyl group; and m is an integer from 1 to 3:

[0026] wherein R⁷ and R⁸ are the same or different and are each an alkylgroup; R⁹ and R¹⁴ are the same or different and are each an alkylenegroup; R¹⁰ and R¹² are the same or different and are each a hydrogenatom or an alkyl group; R¹¹ is one of a hydrogen atom, an alkyl group,an arylgroup, an alkoxy carbonyl group, an aryloxycarbonyl group, and acycloalkyloxycarbonyl group; R¹³ is an alkyl group, an aryl group, or acycloalkyl group; and m is an integer from 1 to 3:

[0027] wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴ and m have the samemeanings as defined above; and

[0028] n is an integer from 1 to 4.

[0029] In Formula (2a), it is preferred that Y is one of a residuederived from a polyol compound (A1) containing no anionic group and aresidue derived from a polyol compound (A2) containing an anionic group;and V combined with Y is an oxygen atom derived from one of a hydroxygroup of the polyol compound (A1) and a hydroxyl group of the polyolcompound (A2), wherein both the residue derived from the polyol compound(A1) and the residue derived from the polyol compound (A2) are containedin the polymer. It is more preferred that Y is one of a residue derivedfrom a polyol compound (A1-1) containing no anionic group and having anumber-average molecular weight of equal to or more than 500, a residuederived from a polyol compound (A1-2) containing no anionic group andhaving a number-average molecular weight of less than 500, and a residuederived from the polyol compound (A2) containing an anionic group; and Vcombined with Y is an oxygen atom derived from one of a hydroxy group ofthe polyol compound (A1-1), a hydroxyl group of the polyol compound(A1-2), and a hydroxyl group of the polyol compound (A2), and whereinall the residue derived from the polyol compound (A1-1), the residuederived from the polyol compound (A1-2), and the residue derived fromthe polyol compound (A2) are contained in the polymer.

[0030] The anionic-group-containing polymer represented by Formula (2)terminally having an alkoxysilyl group can be preferably obtained by,for example, a reaction of an anionic-group-containing polymer with atleast one secondary-amino-group-containing alkoxysilane compound, whichanionic-group-containing polymer being a reaction product among thepolyol compound (A1-1) containing no anionic group and having anumber-average molecular weight of equal to or more than 500; the polyolcompound (A1-2) containing no anionic group and having a number-averagemolecular weight of less than 500; the polyol compound (A2) containingan anionic group; and the polyisocyanate compound (A3), and the at leastone secondary-amino-group containing alkoxysilane compound is selectedfrom alkoxysilane compounds each having one secondary amino grouprepresented by one of following Formulae (3a), (3b), and (3c):

[0031] wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and m have the samemeanings as defined above;

[0032] wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, and m have the samemeanings as defined above;

[0033] wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, and m have the samemeanings as defined above.

BRIEF DESCRIPTION OF THE DRAWINGS

[0034]FIG. 1 is a graph showing infrared absorption spectral data of ahydrophilic compound (1) (a polyethylene glycol having a phenylatedend).

[0035]FIG. 2 is a graph showing infrared absorption spectral data of apolyethylene glycol having a number-average molecular weight of 500.

[0036]FIG. 3 is a graph of the superimposition of the infraredabsorption spectral data of FIG. 1 and the infrared absorption spectraldata of FIG. 2.

[0037]FIG. 4 is a graph showing ¹H-nuclear magnetic resonance spectraldata of the hydrophilic compound (1) (polyethylene glycol having aphenylated end).

[0038]FIG. 5 is a graph showing ¹H-nuclear magnetic resonance spectraldata of the polyethylene glycol having a number-average molecular weightof 500.

BEST MODE FOR CARRYING OUT THE INVENTION

[0039] The anionic-group-containing polymer (A) terminally having analkoxysilyl group is obtained as a result of a reaction among a compound(A1) containing no anionic group and having plural isocyanate-reactivegroups, a compound (A2) having an anionic group and pluralisocyanate-reactive groups, a polyisocyanate compound (A3), andanalkoxysilane compound (A4) containing an isocyanate-reactive group.

[0040] [Compounds (A1) Containing No Anionic Group and Having PluralIsocyanate-Reactive Groups]

[0041] The compound (A1) containing no anionic group and having pluralisocyanate-reactive groups (hereinafter may be referred to as“isocyanate-reactive compound (A1)”) is not specifically limited as longas it is a compound containing no anionic group and having at least twoisocyanate-reactive groups in its molecule. The isocyanate-reactivegroups are not specifically limited, as long as they are groups havingreactivity to isocyanate groups. Such isocyanate-reactive groupsinclude, for example, hydroxyl group, primary amino group (unsubstitutedamino group), secondary amino groups (mono-substituted amino groups),and mercapto group. The plural isocyanate-reactive groups may compriseone type of the isocyanate-reactive group or two or more types of theisocyanate-reactive groups in combination. Hydroxyl group, primary aminogroup, and secondary amino groups are preferred as theisocyanate-reactive group for use in the present invention, of whichhydroxyl group is especially preferred. Accordingly, theisocyanate-reactive compound (A1) can be, for example, polyol compoundscontaining no anionic group, polyamine compounds containing no anionicgroup, and polythiol compounds containing no anionic group, of whichpolyol compounds containing no anionic group and polyamine compoundscontaining no anionic group are preferred. The isocyanate-reactivecompound (A1) can also be compounds each containing no anionic group andhaving a hydroxyl group and an amino group (a primary amino group or asecondary amino group). Each of these isocyanate-reactive compounds (A1)can be used alone or in combination.

[0042] Polyol compounds (A1) containing no anionic group (hereinaftermay be referred to as “polyol(s) (A1)”) as the isocyanate-reactivecompounds (A1) include, for example, polyhydric alcohols, polyetherpolyols, polyester polyols, polycarbonate polyols, polyolefin polyols,polyacrylic polyols, and castor oil.

[0043] In the polyols (A1), the polyhydric alcohols include, but are notlimited to, ethylene glycol, diethylene glycol, propylene glycol,dipropylene glycol, trimethylene glycol, 1,4-tetramethylenediol,1,3-tetramethylenediol, 2-methyl-1,3-trimethylenediol,1,5-pentamethylenediol, neopentyl glycol, 1,6-hexamethylenediol,3-methyl-1,5-pentamethylenediol, 2,4-diethyl-1,5-pentamethylenediol,glycerol, trimethylolpropane, trimethylolethane, cyclohexanediols suchas 1,4-cyclohexanediol, bisphenols such as bisphenol A, and sugaralcohols such as xylitol and sorbitol.

[0044] The polyether polyols include, but are not limited to,polyethylene glycol, polypropylene glycol, polytetramethylene glycol,and other polyalkylene glycols, as well as ethylene oxide-propyleneoxide copolymers, and other copolymers each containing plural alkyleneoxides, i.e., an alkylene oxide-another alkylene oxide copolymers.

[0045] The polyester polyols include, but are not limited to,polycondensation products between polyhydric alcohols and polycarboxylicacids; ring-opened polymers of cyclic esters (lactones); and reactionproducts among three components of polyhydric alcohols, polycarboxylicacids, and cyclic esters. In the polycondensation products, thepolyhydric alcohols can be the aforementioned polyhydric alcohols. Thepolycarboxylic acids include, but are not limited to, malonic acid,maleic acid, succinic acid, glutaric acid, adipic acid, suberic acid,azelaic acid, sebacic acid, dodecanedioic acid, and other aliphaticdicarboxylic acids; 1,4-cyclohexanedicarboxylic acid, and otheralicyclic dicarboxylic acids; terephthalic acid, isophthalic acid,orthophthalic acid, 2,6-naphthalenedicarboxylic-acid,para-phenylenedicarboxylic acid, trimellitic acid, and other aromaticdicarboxylic acids. The cyclic esters in the ring-opened polymersinclude, for example, propiolactone, β-methyl-δ-valerolactone, andε-caprolactone. The polyhydric alcohols, polycarboxylic acids, andcyclic esters in the reaction products of the three components includethe aforementioned compounds.

[0046] The polycarbonate polyols include, but are not limited to,reaction products between polyhydric alcohols and phosgene; andring-opened polymers of cyclic carbonic esters such as alkylenecarbonates. More specifically, the polyhydric alcohols in the reactionproducts between the polyhydric alcohols and phosgene can be theaforementioned polyhydric alcohols. In the ring-opened polymers ofcyclic carbonic esters, the alkylene carbonates include, for example,ethylene carbonate, trimethylene carbonate, tetramethylene carbonate,and hexamethylene carbonate. The polycarbonate polyols are not limitedas long as they are compounds having a carbonate bond in their moleculeand terminally having a hydroxyl group. These compounds may have anester bond in addition to a carbonate bond.

[0047] The polyolefin polyols are polyols each containing an olefin as acomponent of a skeleton or principal chain of a polymer or copolymer andcontaining at least two hydroxyl groups in their molecule and preferablyat their end. The olefin just mentioned above can be ethylene,propylene, other α-olefins, and other olefins each terminally having acarbon-carbon double bond at their end; isobutene, and other olefinshaving a carbon-carbon double bond in a portion other than the end; andbutadiene, isoprene, and other dienes.

[0048] The polyacrylic polyols are polyols each containing a (meth)acrylate as a component of a skeleton or principal chain of a polymer orcopolymer and containing at least two hydroxyl groups in their molecule.The (meth)acrylate is preferably any of (meth)acrylicalkyl esters suchas methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate,butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, dodecyl(meth)acrylate, octadecyl (meth)acrylate, and other (meth)acrylic C₁-C₂₀alkyl esters.

[0049] To introduce hydroxyl groups into the molecules of the polyolefinpolyols and polyacrylic polyols, α,β-unsaturated compounds each having ahydroxyl group can be used as a comonomer with the olefin or(meth)acrylate. Such α,β-unsaturated compounds each having a hydroxylgroup include, for example, 2-hydroxyethyl (meth)acrylate,3-hydroxypropyl (meth)acrylate, and other (meth)acrylic hydroxyalkylesters.

[0050] As the polyols (A1), polyether polyols, polyester polyols, andpolycarbonate polyols can be advantageously used.

[0051] The polyamine compounds containing no anionic group and thepolythiol compounds containing no anionic group as theisocyanate-reactive compounds (A1) include, for example, polyaminecompounds containing no anionic group and polythiol compounds containingno anionic group corresponding to the polyol compounds (A1) containingno anionic group.

[0052] In the present invention, the combination use of anisocyanate-reactive compound (A1-1) having a number-average molecularweight of equal to or more than 500 and an isocyanate-reactive compound(A1-2) having a number-average molecular weight of less than 500 as theisocyanate-reactive compounds (A1) is especially preferred. By using thehigh-molecular-weight isocyanate-reactive compound (A1-1) in combinationwith the low-molecular-weight isocyanate-reactive compound (A1-2), theresulting water-based solid adhesive can bond adherends by contactbonding further satisfactorily.

[0053] The number-average molecular weight of the isocyanate-reactivecompound (A1-1) having a number-average molecular weight of equal to ormore than 500 (hereinafter may be referred to as “isocyanate-reactivecompound (A1-1)”) is not specifically limited in its upper limit, aslong as it is equal to or more than 500, and is preferably in a rangefrom 500 to 10000 and more preferably in a range from 500 to 3000.

[0054] When the isocyanate-reactive compound (A1-1) is, for example, apolyol compound (A1-1) containing no an-ionic group (hereinafter may bereferred to as “polyol compound (A1-1)”), the isocyanate-reactivecompound (A1-1) can be any of the polyol compounds (A1) containing noanionic group and having a number-average molecular weight of equal toor more than 500. More specifically, the polyol compounds (A1-1) as theisocyanate-reactive compounds (A1-1) include, for example, polyetherpolyols each having a number-average molecular weight of equal to ormore than 500, polyester polyols each having a number-average molecularweight of equal to or more than 500, polycarbonate polyols each having anumber-average molecular weight of equal to or more than 500, polyolefinpolyols each having a number-average molecular weight of equal to ormore than 500, and polyacrylic polyols each having a number-averagemolecular weight of equal to or more than 500, selected from among theaforementioned compounds.

[0055] The number-average molecular weight of the isocyanate-reactivecompound (A1-2) having a number-average molecular weight of less than500 (hereinafter may be referred to as “isocyanate-reactive compound(A1-2)”) is not specifically limited in its lower limit, as long as itis less than 500, and is preferably in a range equal to or more than 48and less than 500, and more preferably in a range equal to or more than62 and less than or equal to 300.

[0056] When the isocyanate-reactive compound (A1-2) is, for example, apolyol compound (A1-2) containing no anionic group (hereinafter may bereferred to as “polyol compound (A1-2)”), the isocyanate-reactivecompound (A1-2) can be any of the polyol compounds (A1) containing noanionic group and having a number-average molecular weight less than500. More specifically, the polyol compounds (A1-2) as theisocyanate-reactive compounds (A1-2) include, for example, thepolyhydric alcohols such as ethylene glycol, diethylene glycol,propylene glycol, dipropylene glycol, trimethylene glycol,1,4-tetramethylenediol, 1,3-tetramethylenediol,2-methyl-1,3-trimethylenediol, 1,5-pentamethylenediol, neopentyl glycol,1,6-hexamethylenediol, 3-methyl-1,5-pentamethylenediol,2,4-diethyl-1,5-pentamethylenediol, glycerol, trimethylolpropane,trimethylolethane, cyclohexanediols such as 1,4-cyclohexanediol,bisphenols such as bisphenol A, and sugar alcohols such as xylitol andsorbitol; polyether polyols each having a number-average molecularweight less than 500; polyester polyols each having a number-averagemolecular weight less than 500; polycarbonate polyols each having anumber-average molecular weight less than 500; polyolefin polyols eachhaving a number-average molecular weight less than 500; and polyacrylicpolyols each having a number-average molecular weight less than 500.

[0057] The isocyanate-reactive compound (A1-2) for use in the presentinvention can also be polyamine compounds (A1-2) each having anumber-average molecular weight less than 500 and containing no anionicgroup (hereinafter may be referred to as “polyamine compound(s)(A1-2)”). Such polyamine compounds (A1-2) include, for example,aliphatic polyamines, alicyclic polyamines, aromatic polyamines,aromatic-aliphatic polyamines, hydrazine and derivatives thereof.

[0058] The aliphatic polyamines include, but are not limited to,ethylenediamine, 1,3-trimethylenediamine, 1,4-tetramethylenediamine,1,3-pentamethylenediamine, 1,5-pentamethylenediamine,1,6-hexamethylenediamine, 1,2-propylenediamine, 1,2-butylenediamine,2,3-butylenediamine, 1,3-butylenediamine,2-methyl-1,5-pentamethylenediamine, 3-methyl-1,5-pentamethylenediamine,2,4,4-trimethyl-1,6-hexamethylenediamine,2,2,4-trimethyl-1,6-hexamethylenediamine, and other aliphatic diamines,as well as diethylenetriamine, triethylenetetramine,tetraethylenepentamine, and pentaethylenehexamine.

[0059] The alicyclic polyamines include, but are not limited to,1,3-cyclopentanediamine, 1,4-cyclohexanediamine, 1,3-cyclohexanediamine,1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane,1-amino-1-methyl-4-aminomethylcyclohexane,1-amino-1-methyl-3-aminomethylcyclohexane,4,4′-methylenebis(cyclohexylamine),4,4′-methylenebis(3-methyl-cyclohexylamine),methyl-2,3-cyclohexanediamine, methyl-2,4-cyclohexanediamine,methyl-2,6-cyclohexanediamine, 1,3-bis(aminomethyl)cyclohexane,1,4-bis(aminomethyl)cyclohexane, isophoronediamine, norbornanediamine,and other alicyclic diamines.

[0060] The aromatic polyamines include, but are not limited to,m-phenylenediamine, p-phenylenediamine, 2,4-tolylenediamine,2,6-tolylenediamine, naphthylene-1,4-diamine, naphthylene-1,5-diamine,4,4′-diphenyldiamine, 4,4′-diphenylmethanediamine,2,4′-diphenylmethanediamine, 4,4′-diphenyl ether diamine,2-nitrodiphenyl-4,4′-diamine, 2,2′-diphenylpropane-4,4′-diamine,3,3′-dimethyldiphenylmethane-4,4′-diamine, 4,4′-diphenylpropanediamine,3,3′-dimethoxydiphenyl-4,4′-diamine, and other aromatic diamines.

[0061] The aromatic-aliphatic polyamines include, but are not limitedto, 1,3-xylylenediamine, 1,4-xylylenediamine,α,α,α′,α′-tetramethyl-1,3-xylylenediamine,α,α,α′,α′-tetramethyl-1,4-xylylenediamine,ω,ω′-diamino-1,4-diethylbenzene, 1,3-bis(1-amino-1-methylethyl)benzene,1,4-bis (1-amino-1-methylethyl)benzene,1,3-bis(α,α-dimethylaminomethyl)benzene, and other aromatic-aliphaticdiamines.

[0062] The hydrazine and derivatives thereof include, for example,hydrazine, and dihydrazide compounds. Such dihydrazide compoundsinclude, but are not limited to, carbodihydrazide (carbohydrazide),oxalic acid dihydrazide, malonic acid dihydrazide, succinic aciddihydrazide, glutaric acid dihydrazide, adipic acid dihydrazide, andother aliphatic dicarboxylic acids dihydrazides; isophthalic aciddihydrazide, terephthalic acid dihydrazide, and other aromaticdicarboxylic acids dihydrazides; 1,4-cyclohexanedicarboxylic aciddihydrazide, and other alicyclic dicarboxylic acids dihydrazides.

[0063] Each of the isocyanate-reactive compounds (A1-2) and theisocyanate-reactive compounds (A1-2) can be used alone or incombination, respectively. For example, when a polyamine compound (A1-2)is used as the isocyanate-reactive compound (A1-2), a polyol compound(A1-2) can also be used in combination with the polyamine compound(A1-2). In this case, the ratio of the polyamine compound (A1-2) to thepolyol compound (A1-2) is not specifically limited and can beappropriately set depending on, for example, the type of the targetwater-based solid adhesive.

[0064] The ratio of the isocyanate-reactive compound (A1-1) to theisocyanate-reactive compound (A1-2) is not specifically limited. Toenable the water-based solid adhesive to perform contact bonding, theratio is preferably such that the ratio of the isocyanate-reactivegroups, such as hydroxyl groups, of the isocyanate-reactive compound(A1-1) to the isocyanate-reactive groups, such as hydroxyl groups, ofthe isocyanate-reactive compound (A1-2) is from about 0.05 to about 4.

[0065] [Compounds (A2) Having an Anionic Group and PluralIsocyanate-Reactive Groups]

[0066] The compound (A2) having an anionic group and pluralisocyanate-reactive groups (hereinafter may be referred to as“isocyanate-reactive compound (A2)”) is not specifically limited as longas it is a compound having at least one anionic group and at least twoisocyanate-reactive groups in its molecule. The anionic group in theisocyanate-reactive compound (A2) is preferably carboxyl group and sulfogroup, of which carboxyl group is especially preferred. Theisocyanate-reactive groups in the isocyanate-reactive compound (A2) arenot specifically limited, as long as they are groups having reactivityto isocyanate groups, and include, for example, hydroxyl group, primaryamino group (unsubstituted amino group), secondary amino groups(mono-substituted amino groups), and mercapto group. The pluralisocyanate-reactive groups may comprise one type of theisocyanate-reactive group or two or more types of theisocyanate-reactive groups in combination. As the isocyanate-reactivegroup for use in the present invention, hydroxyl group, primary aminogroup, and secondary amino groups are preferred, of which hydroxyl groupis especially preferred. Accordingly, the isocyanate-reactive compound(A2) can be, for example, any of polyol compounds containing an anionicgroup, polyamine compounds containing an anionic group, and polythiolcompounds containing an anionic group, of which polyol compoundscontaining an anionic group are preferred. The isocyanate-reactivecompound (A2) can also be compounds each containing an anionic group andhaving a hydroxyl group and an amino group (a primary amino group or asecondary amino group). Each of these isocyanate-reactive compounds (A2)can be used alone or in combination.

[0067] Polyol compounds (A2) containing an anionic group (hereinaftermay be referred to as “polyol(s) (A2)”) as the isocyanate-reactivecompounds (A2) include, for example, polyols containing a carboxyl groupcorresponding to the polyols exemplified in the polyols (A1) except withan introduced carboxyl group. The polyols (A2) for use in the presentinvention are preferably polyols having an anionic group and having alow molecular weight, of which polyhydroxy carboxylic acids representedby following Formula (4) are especially preferred.

(HO)_(X)L(COOH)_(Y)   (4)

[0068] In Formula (4), L is a hydrocarbon moiety containing 1 to 12carbon atoms; X is an integer equal to or more than 2; and Y is aninteger equal to or more than 1.

[0069] In Formula (4), the hydrocarbon moiety L is preferably analiphatic hydrocarbon moiety and maybe a straight or branched chain. Xand Y may be the same or different. The two or more hydroxyl groups maybe combined with the same carbon atom or with different carbon atoms.When Y is equal to or more than 2, the two or more carboxyl groups maybe combined with the same carbon atom or with different carbon atoms.

[0070] Of these polyhydroxycarboxylic acids, dimethylolalkanoic acidsare preferred, of which 2,2-dimethylolalkanoic acids are especiallypreferred. Such dimethylol alkanoic acids include, but are not limitedto, 2,2-dimethylolpropionic acid, 2,2-dimethylolbutanoic acid,2,2-dimethylolpentanoic acid, 2,2-dimethylolhexanoic acid,2,2-dimethylolheptanoic acid, 2,2-dimethyloloctanoic acid,2,2-dimethylolnonanoic acid, and 2,2-dimethyloldecanoic acid.

[0071] The anionic-group-containing polyamine compounds andanionic-group-containing polythiol compounds as the isocyanate-reactivecompounds (A2) include anionic-group-containing polyamine compoundscorresponding to the anionic-group-containing polyol compounds (A2),such as polyaminecarboxylic acids corresponding to thepolyhydroxycarboxylic acids represented by Formula (4), andanionic-group-containing polythiol compounds corresponding to theanionic-group-containing polyol compounds (A2), such aspolythiolcarboxylic acids corresponding to the polyhydroxycarboxylicacids represented by Formula (4).

[0072] [Polyisocyanate Compounds (A3)]

[0073] The polyisocyanate compound (A3) (hereinafter may be referred toas “polyisocyanate(s) (A3)”) is not specifically limited as long as itis a compound having at least two isocyanate groups in its molecule.Such polyisocyanates (A3) include, for example, aliphaticpolyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates,and aromatic-aliphatic polyisocyanates. Each of these polyisocyanates(A3) can be used alone or in combination.

[0074] The aliphatic polyisocyanates include, but are not limited to,1,3-trimethylene diisocyanate, 1,4-tetramethylene diisocyanate,1,3-pentamethylene diisocyanate, 1,5-pentamethylene diisocyanate,1,6-hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylenediisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate,2-methyl-1,5-pentamethylene diisocyanate, 3-methyl-1,5-pentamethylenediisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate,2,2,4-trimethyl-1,6-hexamethylene diisocyanate, 2,6-diisocyanate methylcaproate, lysine diisocyanate, and other aliphatic diisocyanates.

[0075] The alicyclic polyisocyanates include, but are not limited to,1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate,1,3-cyclohexane diisocyanate,3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate,4,4′-methylenebis(cyclohexyl isocyanate), methyl-2,4-cyclohexanediisocyanate, methyl-2,6-cyclohexane diisocyanate,1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate,norbornane diisocyanate, and other alicyclic diisocyanates.

[0076] The aromatic polyisocyanates include, but are not limited to,m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylenediisocyanate, 2,6-tolylene diisocyanate, naphthylene-1,4-diisocyanate,naphthylene-1,5-diisocyanate, 4,4′-diphenyl diisocyanate,4,4′-diphenylmethane diisocyanate, 2,4′-diphenylmethane diisocyanate,4,4′-diphenyl ether diisocyanate, 2-nitrodiphenyl-4,4′-diisocyanate,2,2′-diphenylpropane-4,4′-diisocyanate,3,3′-dimethyldiphenylmethane-4,4′-diisocyanate, 4,4′-diphenylpropanediisocyanate, 3,3′-dimethoxydiphenyl-4,4′-diisocyanate, and otheraromatic diisocyanates.

[0077] The aromatic-aliphatic polyisocyanates include, but are notlimited to, 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate,ω,ω′-diisocyanato-1,4-diethylbenzene,1,3-bis(1-isocyanato-1-methylethyl)benzene,1,4-bis(1-isocyanato-1-methylethyl)benzene,1,3-bis(α,α-dimethylisocyanatomethyl)benzene, and otheraromatic-aliphatic diisocyanates.

[0078] Preferred examples of the polyisocyanates (A3) are1,6-cyclohexane diisocyanate, 4,4′-methylenebis(cyclohexyl isocyanate),1,3-bis(isocyanatomethyl)cyclohexane,1,4-bis(isocyanatomethyl)cyclohexane, isophorone diisocyanate,2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate,4,4′-diphenylmethane diisocyanate, 1,3-xylylene diisocyanate,1,4-xylylene diisocyanate, norbornane diisocyanate, and 1,3-bis(α,α-dimethylisocyanatomethyl)benzene. By using any of the aliphaticpolyisocyanates and aromatic-aliphatic polyisocyanates as thepolyisocyanate (A3), resins with less discoloration can be obtained.

[0079] The polyisocyanates (A3) for use in the present invention alsoinclude dimers, trimers, reaction products, and polymers derived fromthe aforementioned aliphatic polyisocyanates, alicyclic polyisocyanates,aromatic polyisocyanates, and aromatic-aliphatic polyisocyanates. Suchcompounds include, for example, dimers and trimers of diphenylmethanediisocyanate, reaction products of trimethylolpropane with tolylenediisocyanate, reaction products of trimethylolpropane with hexamethylenediisocyanate, polymethylene polyphenyl isocyanates, polyetherpolyisocyanates, and polyester polyisocyanates.

[0080] Diisothiocyanate compounds, such as phenyl diisothiocyanate, canbe used in combination with the polyisocyanates (A3) in the presentinvention.

[0081] [Alkoxysilane Compounds (A4) Containing an Isocyanate-ReactiveGroup]

[0082] The alkoxysilane compound (A4) containing an isocyanate-reactivegroup (hereinafter may be referred to as “alkoxysilane(s) (A4)containing an isocyanate-reactive group”) is not specifically limited aslong as it is a silane compound having at least one isocyanate-reactivegroup and at least one alkoxy group in its molecule. Each of thesealkoxysilanes (A4) containing an isocyanate-reactive group can be usedalone or in combination.

[0083] The isocyanate-reactive group is not specifically limited as longas it is a group having reactivity to isocyanate groups and includes,for example, primary amino group (unsubstituted amino group), secondaryamino groups (mono-substituted amino groups), mercapto group, isocyanategroup, and hydroxyl group, of which primary or secondary amino groupsand mercapto group are preferred. When the alkoxysilane (A4) has pluralisocyanate-reactive groups, the plural isocyanate-reactive groups maycomprise one type of isocyanate-reactive group or two or more types ofisocyanate-reactive groups in combination.

[0084] Preferred examples of the alkoxysilanes (A4) containing anisocyanate-reactive group for use in the present invention arealkoxysilane compounds (A4-1) each containing a primary or secondaryamino group, and alkoxysilane compounds (A4-2) each containing amercapto group.

[0085] The alkoxysilane compounds (A4-1) each containing a primary orsecondary amino group (hereinafter may be referred to as“amino-group-containing alkoxysilane(s) (A4-1)”) are not specificallylimited, as long as they are silane compounds each having at least oneprimary or secondary amino group and at least one alkoxy group in theirmolecule. The amino-group-containing alkoxysilanes (A4-1) can each haveone or more tertiary amino groups as amino groups. The alkoxysilanecompounds (A4-2) each containing a mercapto group (hereinafter may bereferred to as “mercapto-group-containing alkoxysilane(s) (A4-2)”) arenot specifically limited as long as they are silane compounds eachhaving at least one mercapto group and at least one alkoxy group intheir molecule.

[0086] Preferred examples of the alkoxy group in the alkoxysilanes (A4)containing an isocyanate-reactive group are methoxy group, ethoxy group,propoxy group, isopropoxy group, butoxy group, isobutyloxy group,s-butyloxy group, t-butyloxy group, and other C₁-C₄ alkoxy groups, ofwhich methoxy group, ethoxy group, and propoxy group are more preferred.Among them, methoxy group and ethoxy group are especially preferred. Thealkoxy groups are generally combined with silicon atoms of thealkoxysilane (A4) containing an isocyanate-reactive group, and thenumber of the alkoxy groups is generally from one to three, andpreferably two or three. Each of these alkoxy groups can be used aloneor in combination. Namely, the alkoxysilane (A4) containing anisocyanate-reactive group may have the same alkoxy group or may have twoor more different alkoxy groups combined with its silicon atom.

[0087] When the isocyanate-reactive groups are amino groups, secondaryamino groups or tertiary amino groups may be constituted by having asubstituent such as a hydrocarbon group. Such hydrocarbon groupsinclude, for example, phenyl group and other aryl groups; methyl group,ethyl group, propyl group, butyl group, and other alkyl groups;cyclohexyl groups and other cycloalkyl groups. The hydrocarbon group mayhave another substituent. Such substituents include, for example, alkoxygroups, aryloxy groups, cycloalkyloxy groups, alkoxycarbonyl groups,aryloxycarbonyl groups, cycloalkyloxycarbonyl groups, and acyl groups.

[0088] The isocyanate-reactive groups such as primary amino group,secondary amino groups, or mercapto group may be directly combined witha silicon atom but are preferably combined with a silicon atom through adivalent group. Such divalent groups include, but are not limited to,alkylene groups, arylene groups, alkylene-arylene groups,alkylene-arylene-alkylene groups, and other divalent hydrocarbon groupseach comprising hydrocarbon group(s) alone; alkylene-oxy-alkylenegroups, alkylene-carbonyl-oxy-alkylene groups,alkylene-oxy-carbonyl-alkylene groups, alkylene-poly(oxyalkylene)groups, and other divalent groups each comprising a hydrocarbon group incombination with another group such as oxy group and carbonyl-oxy group.

[0089] When the alkoxysilane (A4) containing an isocyanate-reactivegroup is, for example, an amino-group-containing alkoxysilane (A4-1),the amino group may be in the form of an aminoalkyl group. Suchaminoalkyl groups include, but are not limited to, aminomethyl group,1-aminoethyl group, 2-aminoethyl group, 1-aminopropyl group,2-aminopropyl group, 3-aminopropyl group, and other amino-C₁-C₃ alkylgroups, corresponding secondary amino groups such as amino-C₁-C₃ alkylgroups which amino group has one hydrocarbon group as a substituent, andtertiary amino groups such as amino-C₁-C₃ alkyl groups which amino grouphas two hydrocarbon groups as substituents. The hydrocarbon groups andother substituents substituted on nitrogen atoms in the secondary aminogroups and tertiary amino groups may each have another amino group, andthe amino group just mentioned above may also have a substituent such asa hydrocarbon group. Namely, the aminoalkyl groups can beN-aminoalkyl-aminoalkyl groups andN-[N-(aminoalkyl)aminoalkyl]aminoalkyl groups. These compounds may havea secondary amino group in addition to a primary amino group. The numberof the primary or secondary amino group(s) is not specifically limitedand is generally one or two. Thus, preferred examples of theamino-group-containing alkoxysilanes (A4-1) are amino-group-containingalkoxysilanes each having at least one secondary amino group, whereinthese alkoxysilanes preferably contain no primary amino group when theyeach contain one secondary amino group, such as compounds represented byfollowing Formula (5c).

[0090] More specifically, preferred examples of theamino-group-containing alkoxysilanes (A4-1) as the alkoxysilanes (A4)containing an isocyanate-reactive group are amino-group-containingalkoxysilanes represented by following Formula (5a) each having aprimary amino group alone as the isocyanate-reactive group,amino-group-containing alkoxysilanes represented by following Formula(5b) each having a primary amino group and a secondary amino group asthe isocyanate-reactive group, and amino-group-containing alkoxysilanesrepresented by following Formula (5c) each having a secondary aminogroup alone as the isocyanate-reactive group. Preferred examples of themercapto-group-containing alkoxysilanes (A4-2) as the alkoxysilanes (A4)containing an isocyanate-reactive group are mercapto-group-containingalkoxysilanes represented by following Formula (5d) each having amercapto group alone as the isocyanate-reactive group.

[0091] In Formulae (5a), (5b), (5c), and (5d), R⁷ and R⁸ are the same ordifferent and are each an alkyl group; R⁹ and R¹⁴ are each an alkylenegroup; R¹⁵ is an aryl group, an alkyl group or a cycloalkyl group; and mis an integer from 1 to 3, wherein the alkylene groups R⁹ and R¹⁴ inFormula (5b) may be the same or different.

[0092] In Formulae (5a), (5b), (5c), and (5d), preferred alkyl groups asR⁷ are, for example, methyl group, ethyl group, propyl group, isopropylgroup, butyl group, isobutyl group, t-butyl group, and other alkylgroups each containing about 1 to about 4 carbon atoms. The alkyl groupas R⁸ can be similar alkyl groups as R⁷, of which methyl group and ethylgroup are preferred. The alkylene group as R⁹ is preferably methylenegroup, ethylene group, trimethylene group, and other alkylene groupseach containing about 1 to about 3 carbon atoms. The alkylene group asR¹⁴ can be any of alkylene groups each containing about 1 to about 3carbon atoms, as in the alkylene group as R⁹. In R¹⁵, the aryl group ispreferably phenyl group; the alkyl group is preferably methyl group,ethyl group, propyl group, isopropyl group, butyl group, isobutyl group,t-butyl group, and other alkyl groups each containing about 1 to about 4carbon atoms; and the cycloalkyl group is preferably cyclohexyl group.The number m is an integer from 1 to 3.

[0093] Examples of the amino-group-containing alkoxysilanes representedby Formula (5a) each having a primary amino group alone as theisocyanate-reactive group are amino methyltrimethoxysilane,aminomethyltriethoxysilane, β-aminoethyltrimethoxysilane,β-aminoethyltriethoxysilane, γ-aminopropyltrimethoxysilane,γ-aminopropyltriethoxysilane, γ-aminopropyltripropoxysilane,γ-aminopropyltriisopropoxysilane, γ-aminopropyltributoxysilane, andother aminoalkyltrialkoxysilanes; β-aminoethylmehyldimethoxysilane,β-aminoethylmethyldiethoxysilane, γ-aminopropylmethyldimethoxysilane,γ-aminopropylmethyldiethoxysilane, γ-aminopropylmethyldipropoxysilane,and other (aminoalkyl)alkyldialkoxysilanes, and correspondingaminoalkyldialkyl(mono)alkoxysilanes.

[0094] Examples of the amino-group-containing alkoxysilanes representedby Formula (5b) each having a primary amino group and a secondary aminogroup as the isocyanate-reactive group areN-β(aminoethyl)-γ-aminopropyltrimethoxysilane,N-β(aminoethyl)-γ-aminopropyltriethoxysilane, and otherN-(aminoalkyl)aminoalkyltrialkoxysilanes;N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane,N-β(aminoethyl)-γ-aminopropylmethyldiethoxysilane, and otherN-(aminoalkyl)aminoalkylalkyldialkoxysilanes.

[0095] Examples of the amino-group-containing alkoxysilanes representedby Formula (5c) each having a secondary amino group alone as theisocyanate-reactive group are N-phenyl-β-aminoethyltrimethoxysilane,N-phenyl-β-aminoethyltriethoxysilane, and otherN-phenyl-β-aminoethyltrialkoxysilanes;N-phenyl-γ-aminopropyltrimethoxysilane,N-phenyl-γ-aminopropyltriethoxysilane,N-phenyl-γ-aminopropyltripropoxysilane,N-phenyl-γ-aminopropyltributoxysilane, and otherN-phenyl-γ-aminopropyltrialkoxysilanes, N-phenylaminoalkyl(mono- ordi-)alkyl(di- or mono-)alkoxysilanes corresponding to thesealkoxysilanes, as well as N-alkylaminoalkyltrialkoxysilanescorresponding to the amino-group-containing alkoxysilanes containing asecondary amino group with a phenyl group as a substituent, such asN-methyl-3-aminopropyltrimethoxysilane,N-ethyl-3-aminopropyltrimethoxysilane,N-n-propyl-3-aminopropyltrimethoxysilane,N-n-butyl-aminomethyltrimethoxysilane,N-n-butyl-2-aminoethyltrimethoxysilane,N-n-butyl-3-aminopropyltrimethoxysilane,N-n-butyl-3-aminopropyltriethoxysilane, andN-n-butyl-3-aminopropyltripropoxysilane, as well as correspondingN-alkylaminoalkyl(mono- or di-)alkyl(di- or mono-)alkoxysilanes.

[0096] The amino-group-containing alkoxysilanes (A4-1) for use in thepresent invention are also commercially available under the trade namesof “KBM6063”, “X-12-896”, “KBM576”, “X-12-565”, “X-12-580”, “X-12-5263”,“X-12-666”, “KBM 6123”, “X-12-575”, “X-12-577”, “X-12-563B”, “X-12-730”,“X-12-562”, “X-12-5202”, “X-12-5204”, and “KBE 9703” from Shin-EtsuChemical Co., Ltd. The amino-group-containing alkoxysilanes (A4-1)therefore also include N-(5-aminopentyl)-γ-aminopropyltrimethoxysilane,N-β[N-β(aminoethyl)aminoethyl]-γ-aminopropyltrimethoxysila ne,1,2-bis(γ-trimethoxysilyl-propylamino)ethane,bis(y-trimethoxysilyl-propyl)amine,N-β(aminoethyl)-β(4-aminomethylphenyl)ethyltrimethoxysilan e, andcorresponding alkoxysilane compounds each having a hydrocarbon groupsuch as an alkyl group or an alkylene group containing a differentnumber of carbon atoms; alkoxysilane compounds each having another groupsuch as a styrenically unsaturated group, an olefinically unsaturatedgroup, or a carboxyl group in addition to a primary or secondary aminogroup; alkoxysilane compounds in the form of a salt, such as ahydrochloride, having a primary or secondary amino group; andalkoxysilane compounds each having plural alkoxysilyl groups in additionto a primary or secondary amino group.

[0097] Examples of the mercapto-group-containing alkoxysilanesrepresented by Formula (5d) each having a mercapto group alone as theisocyanate-reactive group are mercaptomethyltrimethoxysilane,mercaptomethyltriethoxysilane, β-mercaptoethyltrimethoxysilane,β-mercaptoethyltriethoxysilnane, γ-mercaptopropyltrimethoxysilane,γ-mercaptopropyltriethoxysilane, γ-mercaptopropyltripropoxysilane,γ-mercaptopropyltriisopropoxysilane, γ-mercaptopropyltributoxysilane,and other mercaptoalkyltrialkoxysilanes;β-mercaptoethylmethyldimethoxysilane,β-mercaptoethylmethyldiethoxysilane,γ-mercaptopropylmethyldimethoxysilane,γ-mercaptopropylmethyldiethoxysilane,γ-mercaptopropylmethyldipropoxysilane, other(mercaptoalkyl)alkyldialkoxysilanes, and correspondingmercaptoalkyldialkyl(mono)alkoxysilanes.

[0098] The amino-group-containing alkoxysilanes (A4-1) are preferablyused as the isocyanate-reactive group-containing alkoxysilanes (A4) fortheir easy reactions and commercial availability. Among suchamino-group-containing alkoxysilanes (A4-1), preferredamino-group-containing alkoxysilanes having at least a primary aminogroup (e.g., a primary amino group alone or a primary amino group and asecondary amino group) as the isocyanate-reactive group are, forexample, N-β-aminoethyl-γ-aminopropyltrimethoxysilane,N-β(aminoethyl)-γ-aminopropyltriethoxysilane,N-β(aminoethyl)-γ-aminorpopylmethyldimethoxysilane, andγ-aminopropyltrimethoxysilane. Preferred amino-group-containingalkoxysilanes having a secondary amino group alone as theisocyanate-reactive group are, for example,N-phenylγ-aminopropyltrimethoxysilane, andN-n-butyl-3-aminopropyltrimethoxysilane.

[0099] The amino-group-containing alkoxysilanes (A4-1) can also bealkoxysilane compounds having at least a secondary amino group as theisocyanate-reactive group obtained in the following manner (hereinaftermay be referred to as “ester-modified amino-group-containingalkoxysilanes (A4-5)”). These ester-modified amino-group-containingalkoxysilanes (A4-5) are obtained as a result of a reaction between analkoxysilane compound having at least a primary amino group, preferablyboth primary and secondary amino groups, as the isocyanate-reactivegroup (hereinafter may be referred to as “primary amino group-containingalkoxysilane”) as mentioned above and an unsaturated carboxylic ester(A5). Such unsaturated carboxylic esters (A5) for use in the preparationof the ester-modified amino-group-containing alkoxysilanes (A4-5) arenot specifically limited as long as they are compounds in which at leastone of, and preferably all of, the carboxylic acid groups (carboxylgroups) of an unsaturated carboxylic acid forms an ester. Theunsaturated carboxylic esters (A5) can be any of unsaturatedmonocarboxylic esters and unsaturated polycarboxylic esters such asunsaturated dicarboxylic esters. Each of these unsaturated carboxylicesters (A5) can be used alone or in combination.

[0100] Preferred examples of the unsaturated carboxylic esters (A5) arecompounds each having a carboxyl group or its ester directly combinedwith a carbon atom constituting a carbon-carbon double bond. Such estersof carboxyl group include, for example, alkoxycarbonyl groups,cycloalkyloxycarbonyl groups, and aryloxycarbonyl groups. Such compoundsinclude, for example, acrylic esters, methacrylic esters, crotonicesters, isocrotonic esters, 2-butenoic esters, 3-methyl-2-butenoicesters, 2-pentenoic esters, 2-octenoic esters, cinnamic esters, andother esters of unsaturated monocarboxylic acids; maleic esters (mono-or di-esters), fumaric esters (mono- or di-esters), itaconic esters(mono- or di-esters), and other esters of unsaturated dicarboxylicacids.

[0101] The ester moieties in the unsaturated carboxylic esters (A5)include, but are not limited to, methyl esters, ethyl esters,propylesters, isopropylesters, butylesters, isobutylesters, s-butylesters, t-butyl esters, pentyl esters, isopentyl esters, hexyl esters,heptyl esters, octyl esters, 2-ethylhexyl esters, nonyl esters, decylesters, isodecyl esters, undecyl esters, dodecyl esters, tridecylesters, tetradecyl esters, hexadecyl esters, octadecyl esters, and otheraliphatic hydrocarbon esters such as alkyl esters; cyclohexyl esters,isobornyl esters, bornyl esters, dicyclopentadienyl esters,dicyclopentanyl esters, dicyclopentenyl esters, tricyclodecanyl esters,and other alicyclic hydrocarbon esters such as cycloalkyl esters; phenylesters, benzyl esters, and other aromatic hydrocarbon esters such asaryl esters. When the unsaturated carboxylic esters each have pluralester moieties, these ester moieties may be the same or different.

[0102] Among these unsaturated carboxylic esters, acrylic esters,methacrylic esters (hereinafter may be generically referred to as“(meth)acrylicesters”), and maleic diesters are preferred as theunsaturated carboxylic esters (A5). Such (meth)acrylic esters include,but are not limited to, methyl (meth)acrylate, ethyl (meth)acrylate,butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate,2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, octadecyl(meth)acrylate, and other (meth)acrylic alkyl esters. The maleicdiestersinclude, but are not limited to, dimethylmaleate, diethyl maleate,dibutyl maleate, dihexyl maleate, dioctyl maleate,di(2-ethylhexyl)maleate, didodecyl maleate, dioctadecyl maleate, andother maleic dialkyl esters.

[0103] More specifically, the alkoxysilane compounds each having atleast a secondary amino group as the isocyanate-reactive group and beingobtained as a result of a primary amino group-containing alkoxysilaneand an unsaturated carboxylic ester (A5), i.e., the ester-modifiedamino-group-containing alkoxysilanes (A4-5) include, for example,compounds in which a carbon atom at the β-position in a carbon-carbondouble bond of the unsaturated carboxylic ester (A5) is combined with atleast a nitrogen atom of the amino group in the primary aminogroup-containing alkoxysilane. Namely, the ester-modifiedamino-group-containing alkoxysilanes (A4-5) are compounds obtained as aresult of a Michael addition reaction of the nitrogen atom of the aminogroup in the primary amino group-containing alkoxysilane to theunsaturated bond (carbon-carbon double bond) of the unsaturatedcarboxylic ester (A5). The reaction can be performed in the presence of,or in the absence of, a solvent. The reaction may be performed withheating and/or with the application of pressure.

[0104] When the primary amino group-containing alkoxysilane is, forexample, an alkoxysilane compound represented by Formula (5a) having aprimary amino group alone as the isocyanate-reactive group, and theunsaturated carboxylic ester (A5) is an unsaturated carboxylic esterrepresented by following Formula (6), the ester-modifiedamino-group-containing alkoxysilanes (A4-5) can be represented byfollowing Formula (3d):

[0105] wherein R¹⁰ and R¹² are the same or different and are each ahydrogen atom or an alkyl group; R¹¹ is a hydrogen atom, an alkyl group,an aryl group, an alkoxycarbonyl group, an aryloxycarbonyl group, or acycloalkyloxycarbonyl group; and R¹³ is an alkyl group, an aryl group ora cycloalkyl group:

[0106] wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, and m have the samemeanings as defined above.

[0107] The ester-modified amino-group-containing alkoxysilanes (A4-5)represented by Formula (3d) each have only one secondary amino group asthe amino group. In the ester-modified amino-group-containingalkoxysilanes (A4-5) represented by Formula (3d), R¹¹ is preferably ahydrogen atom or an alkyl group. Specifically, preferred ester-modifiedamino-group-containing alkoxysilanes (A4-5) represented by Formula (3d)are ester-modified amino-group-containing alkoxysilanes (A4-5)represented by following Formula (3a):

[0108] wherein R⁷, R⁸, R⁹, R¹⁰, R¹², R¹³, and m have the same meaningsas defined above; and R^(11a) is a hydrogen atom or an alkyl group.

[0109] When the primary amino group-containing alkoxysilane is analkoxysilane compound represented by Formula (5b) having a primary andsecondary amino groups as the isocyanate-reactive group, and theunsaturated carboxylic ester (A5) is the unsaturated carboxylic esterrepresented by Formula (6), the ester-modified amino-group-containingalkoxysilanes (A4-5) can be represented by following Formula (3b) or(3c):

[0110] wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, and m have the samemeanings as defined above:

[0111] wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, and m have the samemeanings as defined above.

[0112] These ester-modified amino-group-containing alkoxysilanes (A4-5)represented by Formula (3b) or (3c) each have one secondary amino groupand one tertiary amino group as the amino groups.

[0113] In Formulae (3a), (3b), (3c), (3d), and (6), R⁷, R⁸, R⁹, R¹⁰,R¹¹, R¹², R¹³, R¹⁴, and m have the same meanings as defined above.Specifically, preferred alkyl groups as R⁷ are, for example, methylgroup, ethyl group, propyl group, isopropyl group, butyl group, isobutylgroup, t-butyl group, and other alkyl groups each containing about 1 toabout 4 carbon atoms. The alkyl group as R⁸ can be similar alkyl groupsas R⁷, of which methyl group and ethyl group are preferred. The alkylenegroup as R⁹ is preferably methylene group, ethylene group, trimethylenegroup, and other alkylene groups each containing about 1 to about 3carbon atoms. The alkylene group as R¹⁴ can be any of alkylene groupseach containing about 1 to about 3 carbon atoms, as in the alkylenegroup as R⁹. The number m is an integer from 1 to 3.

[0114] The alkyl group as R¹⁰ includes, but is not limited to, methylgroup, ethyl group, propyl group, butyl group, isobutyl group, t-butylgroup, hexyl group, and other alkyl groups each containing about 1 toabout 6 carbon atoms. The alkyl group as R¹¹ includes, for example,methyl group, ethyl group, and other alkyl groups each containing about1 or 2 carbon atoms. The aryl group as R¹¹ includes phenyl group. In thealkoxycarbonyl group, aryloxycarbonyl group, and cycloalkyloxycarbonylgroup as R¹¹, the alkyl group moiety, aryl group moiety, and cycloalkylgroup moiety are preferably alkyl groups, aryl groups, and cycloalkylgroups exemplified in R¹³ mentioned later. The alkyl group as R¹²includes, for example, methyl group, ethyl group, and other alkyl groupseach containing about 1 or 2 carbon atoms. The alkyl group as R¹³includes, but is not limited, methyl group, ethyl group, propyl group,butyl group, isobutyl group, t-butyl group, hexyl group, octyl group,2-ethylhexyl group, and other alkyl groups each containing about 1 toabout 20 carbon atoms. The aryl group as R¹³ includes phenyl group, andthe cycloalkyl group as R¹³ includes, for example, cyclohexyl group.

[0115] The substituent R^(11a) corresponds to the cases where R¹¹ is ahydrogen atom or an alkyl group. The alkyl group as R^(11a) can beselected from the aforementioned alkyl groups exemplified as R¹¹.

[0116] Preferred amino-group-containing alkoxysilanes (A4-1) for use inthe present invention are alkoxysilane compounds having at least asecondary amino group (mono-substituted amino group), of whichester-modified alkoxysilanes (A4-5) represented by Formula (3a), (3b) or(3c) are especially preferred.

[0117] [Anionic-Group-Containing Polymers (A) Terminally Having anAlkoxysilyl Group]

[0118] The anionic-group-containing polymer (A) terminally having analkoxysilyl group is a reaction product among the isocyanate-reactivecompound (A1), the isocyanate-reactive compound (A2), the polyisocyanate(A3), and the alkoxysilane compound (A4) containing anisocyanate-reactive group, as mentioned above. The polymer (A) has, inits molecule, an anionic group derived from the isocyanate reactivecompound (A2) and, at the end of its principal chain, an alkoxysilylgroup derived from the alkoxysilane (A4) containing anisocyanate-reactive group. The anionic-group-containing polymer (A)terminally having an alkoxysilyl group may have a side chain derivedfrom the unsaturated carboxylic ester according to necessity. Theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup can be, for example, an anionic-group-containing polymer having analkoxysilylated end obtained as a result of a reaction between ananionic-group-containing polymer and the alkoxysilane (A4) containing anisocyanate-reactive group, which anionic-group-containing polymer is areaction product among the isocyanate-reactive compound (A1), theisocyanate-reactive compound (A2), and the polyisocyanate (A3).Preferred examples of such anionic-group-containing polymer (A) havingan alkoxysilylated end obtained as a result of a reaction between ananionic-group-containing polymer-and the alkoxysilane (A4) containing anisocyanate-reactive group, which anionic-group-containing polymer is areaction product among the isocyanate-reactive compound (A1), theisocyanate-reactive compound (A2), and the polyisocyanate (A3), areanionic-group-containing polymers represented by following Formula (2)terminally having an alkoxysilyl group:

WNH —CO—X)_(n)   (2)

[0119] wherein W is a residue corresponding to a skeleton of ananionic-group-containing polymer; the nitrogen atom combined with W is anitrogen atom derived from an isocyanate group at the end of theanionic-group-containing polymer; W has a structural unit represented byfollowing Formula (2a):

NH—CO—V—Y—V—CO—NH-Z  (2a)

[0120] wherein Y is one of a residue derived from the compound (A1)containing no anionic group and having plural isocyanate-reactive groupsand a residue derived from the compound (A2) having an anionic group andplural isocyanate-reactive groups; V combined with Y is a group derivedfrom one of isocyanate-reactive groups of the compound (A1) and thecompound (A2), wherein both the residue derived from the compound (A1)and the residue derived from the compound (A2) as Y are contained in thepolymer; Z is a residue derived from the polyisocyanate compound (A3),wherein a nitrogen atom combined with Z and a nitrogen atom on theopposite side to Z are nitrogen atoms derived from isocyanate groups ofthe polyisocyanate compound (A3);

[0121] X is an alkoxysilyl-containing group represented by any one offollowing Formulae (2b), (2c), and (2d):

[0122] wherein R⁷ and R⁸ are the same or different and are each an alkylgroup; R⁹ is an alkylene group; R¹⁰ and R¹² are the same or differentand are each a hydrogen atom or an alkyl group; R^(11a) is a hydrogenatom or an alkyl group; R¹³ is an alkyl group, an aryl group or acycloalkyl group; and m is an integer from 1 to 3:

[0123] wherein R⁷ and R⁸are the same or different and are each an alkylgroup; R⁹ and R¹⁴ are the same or different and are each an alkylenegroup; R¹⁰ and R¹² are the same or different and are each a hydrogenatom or an alkyl group; R¹¹ is a hydrogen atom, an alkyl group, an arylgroup, an alkoxycarbonyl group, an aryloxycarbonyl group, or acycloalkyloxycarbonyl group; R¹³ is an alkyl group, an aryl group, or acycloalkyl group; and m is an integer from 1 to 3:

[0124] wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, and m have the samemeanings as defined above; and

[0125] n is an integer from 1 to 4.

[0126] Preferred examples of the anionic-group-containing polymers (A)terminally having an alkoxysilyl group for use in the present inventionare anionic-group-containing polymers having an alkoxysilylated end andbeing obtained as a result of a reaction between ananionic-group-containing polymer and the alkoxysilane (A4) containing anisocyanate-reactive group, which anionic-group-containing polymer is areaction product among the polyol (A1) as the isocyanate-reactivecompound (A1), the polyol (A2) as the isocyanate-reactive compound (A2),and the polyisocyanate (A3). Namely, it is preferred in Formula (2a)that Y is one of a residue derived from the polyol compound (A1)containing no anionic group and a residue derived from the polyolcompound (A2) containing an anionic group; and V combined with Y is anoxygen atom derived from a hydroxyl group of the polyol compound (A1)containing no anionic group or a hydroxyl group of the polyol compound(A2) containing an anionic group, wherein both the residue derived fromthe polyol compound (A1) and the residue derived from the polyolcompound (A2) are contained in the polymer.

[0127] Specifically, preferred examples of the anionic-group-containingpolymers having an alkoxysilylated end as the anionic-group-containingpolymers (A) terminally having an alkoxysilyl group areanionic-group-containing polymers represented by following Formula (7)having an alkoxysilyl group at the end, which anionic-group-containingpolymers (A) terminally having an alkoxysilyl group are obtained as aresult of, for example, a reaction between an anionic-group-containingpolymer and the ester-modified amino group-containing alkoxysilane(A4-5) as the alkoxysilane (A4) containing an isocyanate-reactive group,which anionic-group-containing polymer is a reaction product among thepolyol (A1) (polyol compound (A1) containing no anionic group), thepolyol (A2) (polyol compound (A2) containing an anionic group), and thepolyisocyanate (A3).

W¹NH—CO—X)_(n)   (7)

[0128] In Formula (7), W¹ is a residue corresponding to a skeleton of ananionic-group-containing polymer; a nitrogen atom combined with W¹ is anitrogen atom derived from the terminal isocyanate group of theanionic-group-containing polymer, and W¹ has a structural unitrepresented by following Formula (7a)

NH—CO—O—Y¹—O—CO—NH-Z  (7a)

[0129] wherein Y¹ is one of a residue derived from the polyol compound(A1) containing no anionic group and a residue derived from the polyolcompound (A2) containing an anionic group; an oxygen atom combined withY¹ is an oxygen atom derived from a hydroxyl group of one of the polyolcompound (A1) containing no anionic group and the polyol compound (A2)containing an anionic group, wherein both the residue derived from thepolyol compound (A1) containing no anionic group and the residue derivedfrom the polyol compound (A2) containing an anionic group as Y¹ arecontained in the polymer; and X, Z and n have the same meanings asdefined above.

[0130] The moieties W¹ and Y¹ in Formula (7) correspond to W and Y inFormula (2) when the compound (A1) containing no anionic group andhaving plural isocyanate-reactive groups is a polyol compound (A1)containing no anionic group, and the compound (A2) having an anionicgroup and plural isocyanate-reactive groups is a polyol compound (A2)containing an anionic group.

[0131] The residue W in Formula (2), namely the reside W correspondingto the skeleton of the anionic-group-containing polymer has thestructural unit represented by Formula (2a) The residue W thereby has astructural unit derived from the isocyanate-reactive compound (A1) suchas the polyol compound (A1) containing no anionic group, a structuralunit derived from the isocyanate-reactive compound (A2) such as thepolyol compound (A2) containing an anionic group, and a structural unitderived from the polyisocyanate compound (A3). Bonds such as urethanebond and urea bond are formed between the polyisocyanate compound (A3)and the isocyanate-reactive compound (A1), and between thepolyisocyanate compound (A3) and the isocyanate-reactive compound (A2).In other words, V combined with Y in Formula (2a) is a group, such as anoxygen atom (—O— group), an unsubstituted nitrogen atom (—NH-group), ora mono-substituted nitrogen atom, derived from the isocyanate-reactivegroup in a bonding site such as a urethane bond and a urea bond. Thebonding site just mentioned above is formed as a result of the reactionbetween an isocyanate-reactive group of the isocyanate-reactive compound(A1) or of the isocyanate-reactive compound (A2) and an isocyanate groupof the polyisocyanate compound (A3). Two Vs combined with Y may be thesame group or different groups.

[0132] Two nitrogen atoms in Formula (2a), namely, a nitrogen atomcombined with Z and a nitrogen atom on the opposite side to Z, arenitrogen atoms derived from isocyanate groups of the polyisocyanatecompound (A3). A nitrogen atom combined with W in Formula (2) is anitrogen atom derived from an isocyanate group of the polyisocyanatecompound (A3). Namely, the anionic-group-containing polymer relating toW has an isocyanate group at its end, and the nitrogen atom combinedwith W is a nitrogen atom derived from the terminal isocyanate group ofthis anionic-group-containing polymer.

[0133] As X in Formula (2), the alkoxysilyl-containing groupsrepresented by Formulae (2b), (2c), and (2d) are preferred, of whichalkoxysilyl-containing groups represented by Formulae (2c) and (2d) areespecially preferred.

[0134] The number n in Formula (2) is an integer from 1 to 4, preferablyan integer from 1 to 3, and especially preferably 2 or 3.

[0135] It is especially preferred in Formula (2a) that Y is one of aresidue derived from the polyol compound (A1-1) containing no anionicgroup and having a number-average molecular weight of equal to or morethan 500, a residue derived from the polyol compound (A1-2) containingno anionic group and having a number-average molecular weight of lessthan 500, and a residue derived from the polyol compound (A2) containingan anionic group; and V combined with Y is an oxygen atom derived from ahydroxy group of the polyol compound (A1-1), a hydroxyl group of thepolyol compound (A1-2), or a hydroxyl group of the polyol compound (A2),wherein all the residue derived from the polyol compound (A1-1), theresidue derived from the polyol compound (A1-2), and the residue derivedfrom the polyol compound (A2) are contained in the polymer.

[0136] The alkoxysilyl-containing group X represented by one of Formulae(2b), (2c), and (2d) can be introduced by using the ester-modifiedamino-group-containing alkoxysilane (A4-5) represented by one ofFormulae (3a), (3b), and (3c).

[0137] The anionic-group-containing polymer represented by Formula (2)terminally having an alkoxysilyl group may form a salt. For example, itis acceptable that the anionic group in the anionic-group-containingpolymer (A) terminally having an alkoxysilyl group is neutralized withthe basic compound (B) to form a salt of the anionic group, as describedlater. The anionic-group-containing polymer represented by Formula (2)terminally having an alkoxysilyl group may be hydrolyzed. For example,the polymer may be a hydrolyzed polymer having a hydrolyzed alkoxysilylgroup in which the terminal alkoxysilyl group is partially or completelyhydrolyzed with water (C) to thereby form a silanol group and/orsiloxane bond.

[0138] The anionic-group-containing polymer is a reaction product amongthe isocyanate-reactive compound (A1), the isocyanate-reactive compound(A2), and the polyisocyanate (A3) The reaction can be performedaccording to a known or conventional procedure for the preparation of aurethane prepolymer by reaction of a polyisocyanate compound with apolyol compound and/or a polyamine compound. Theanionic-group-containing polymer preferably has an isocyanate group atits end. The polyol (A1) and the polyol (A2) are preferably used as theisocyanate-reactive compound (A1) and the isocyanate-reactive compound(A2), respectively, as described above. Naturally, a polyamine compoundcontaining no anionic group can be used in combination with the polyol(A1) as the isocyanate-reactive compound (A1).

[0139] To accelerate the reaction, a polymerization catalyst can be usedin mixing or in the reaction of the isocyanate-reactive compound (A1),the isocyanate-reactive compound (A2), and the polyisocyanate (A3). Thereaction or mixing procedure can be performed in a solvent.

[0140] The reaction between the anionic-group-containing polymer and thealkoxysilane (A4) containing an isocyanate-reactive group can beperformed by mixing the two components, where necessary, with heating.As a result of the reaction, the terminal isocyanate group of theanionic-group-containing polymer is alkoxysilylated to thereby yield theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup as the anionic-group-containing polymer having an alkoxysilylatedend.

[0141] A polymerization catalyst can be used in the mixing or reactionprocedure as mentioned above. Known or conventional polymerizationcatalysts (curing catalysts) for use, for example, in the reactionbetween a polyisocyanate compound and a polyol compound and/or apolyamine compound can be used as the polymerization catalyst. Morespecifically, such polymerization catalysts include, for example,organotin compounds, metallic complexes, amine compounds and other basiccompounds, and organophosphate compounds. The organotin compoundsinclude, but are not limited to, dibutyltindilaurate, dibutyltinmaleate, dibutyltin phthalate, stannous octanoate, dibutyltin methoxide,dibutyltin diacetylacetate, and dibutyltin diversatates. The metalliccomplexes include, but are not limited to, tetrabutyl titanate,tetraisopropyl titanate, triethanolamine titanate, and other titanatecompounds; lead octanoate, lead naphthenate, nickel naphthenate, cobaltnaphthenate, and other metallic salts of carboxylic acids; aluminumacetylacetonato complex, vanadium acetylacetonato complex, and othermetal acetylacetonato complexes. The amine compounds and other basiccompounds include, but are not limited to,γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and otheraminosilanes; tetramethylammonium chloride, benzalkonium chloride, andother quaternary ammonium salts; DABCO series and DABCO BL series (tradenames) available from Sankyo Air Products Co., Ltd.,1,8-diazabicyclo[5.4.0]undec-7-ene, and other line arorcyclic tertiaryamines and quaternary ammonium salts each containing plural nitrogenatoms. The organophosphate compounds include, but are not limited to,monomethyl phosphate, di-n-butyl phosphate, and triphenyl phosphate.

[0142] A solvent can be used in the mixing or reaction procedure.

[0143] The order of addition of the individual components is notspecifically limited and can be appropriately set according to the typesof the components. However, when the polyol (A1) or the polyol compound(A1-1) and the polyol compound (A1-2) are used as theisocyanate-reactive compound (A1) and the polyamine compound (A1-2) isnot used, the anionic-group-containing polymer (A) terminally having analkoxysilyl group is preferably prepared in the following manner for itsefficient preparation. Initially, the polyisocyanate (A3) is added to amixture of the polyol (A2) with the polyol (A1), or a mixture of thepolyol (A2) with the polyol compound (A1-1) and the polyol compound(A1-2), the resulting mixture is further treated with a polymerizationcatalyst where necessary for reaction to thereby yield theanionic-group-containing polymer, and the reaction mixture is treatedwith the alkoxysilane (A4) containing an isocyanate-reactive group tothereby yield the anionic-group-containing polymer (A) terminally havingan alkoxysilyl group.

[0144] The preparation of the anionic-group-containing polymer (A)terminally having an alkoxysilyl group has been described by using thepolyol (A1) and the polyol (A2) as the isocyanate-reactive compound (A1)and the isocyanate-reactive compound (A2), respectively. Theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup can also be prepared according to a similar procedure by using thepolyamine compound and/or the polythiol compound as theisocyanate-reactive compound (A1) and/or the isocyanate-reactivecompound (A2).

[0145] For example, when the isocyanate-reactive compound (A1-1) and thepolyamine compound (A1-2) as the isocyanate-reactive compound (A1-2) areused as the isocyanate-reactive compounds (A1), the polyamine compound(A1-2) can be added (i) during mixing and reaction among theisocyanate-reactive compound (A1-1), the isocyanate-reactive compound(A1-2), such as the polyol compound (A1-2), other than the polyaminecompound (A1-2), and the polyisocyanate (A3) or after the preparation ofan anionic-group-containing polymer as a result of the reaction amongthe isocyanate-reactive compound (A1-1), the isocyanate-reactivecompound (A1-2), such as the polyol compound (A1-2), other than thepolyamine compound (A1-2), and the polyisocyanate (A3) The polyaminecompound (A1-2) is preferably used (ii) before, during, or after(preferably during or after) the dispersion of ananionic-group-containing polymer having partially alkoxysilylated endinto the water (C) The anionic-group-containing polymer having partiallyalkoxysilylated end is obtained as a result of the reaction between ananionic-group-containing polymer and the alkoxysilane (A4) containing anisocyanate-reactive group, which anionic-group-containing polymer isobtained as a result of the reaction among the isocyanate-reactivecompound (A1-1), the isocyanate-reactive compound (A1-2), such as thepolyol compound (A1-2), other than the polyamine compound (A1-2), andthe polyisocyanate (A3). Namely, the anionic-group-containing polymer(A) terminally having an alkoxysilyl group can be prepared as a resultof the reaction between the anionic-group-containing polymer having apartially alkoxysilylated end and the polyamine compound (A1-2).

[0146] The proportions of the isocyanate-reactive compound (A1), theisocyanate-reactive compound (A2), the polyisocyanate (A3), and thealkoxysilane (A4) containing an isocyanate-reactive group are notspecifically limited in the present invention. For example, the ratio ofthe polyisocyanate (A3) to the isocyanate-reactive compound (A1) and theisocyanate-reactive compound (A2) can be set within such a range thatthe equivalent ratio [NCO/NCO-reactive group] of the isocyanate group inthe polyisocyanate compound (A3) to the isocyanate-reactive groups inthe isocyanate-reactive compound (A1) and the isocyanate-reactivecompound (A2) is more than 1 and less than or equal to 1.5, preferablymore than 1 and less than or equal to 1.3, and more preferably more than1 and less than or equal to 1.2. If the equivalent ratioNCO/NCO-reactive group is excessively high, such as more than 1.5, thewater-based solid adhesive may have deteriorated stability and decreasedcontact bonding property. If the equivalent ratio NCO/NCO-reactive groupis excessively low, such as less than or equal to 1, the silyl group maynot sufficiently be introduced and the water-based solid adhesive mayhave deteriorated adhesion.

[0147] When the isocyanate-reactive compound (A1) and/or theisocyanate-reactive compound (A2) has three or more isocyanate-reactivegroups, each at least two of the isocyanate-reactive groups in theisocyanate-reactive compound (A1) and/or the isocyanate-reactivecompound (A2) may be combined with isocyanate groups of thepolyisocyanate (A3), and residual isocyanate-reactive group(s),specifically hydroxyl group(s), can remain in the form of a free group.

[0148] The proportion of the polyisocyanate (A3) is preferably such thatthe content of isocyanate groups in the anionic-group-containing polymeris from 0.05% to 2.0% by mass, more preferably from 0.1% to 1.5% bymass, and especially preferably from 0.3% to 1.0% by mass. If thecontent of the isocyanate group is excessively high, such as more than2.0% by mass, or is excessively low, such as less than 0.05% by mass,the water-based solid adhesive may have decreased adhesion.

[0149] The proportion of the isocyanate-reactive compound (A2) ispreferably such that the content of anionic groups in theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup is from 0.2% to 5.0% by mass, more preferably from 0.5% to 4.0% bymass, and especially preferably from 0.8% to 3.5% by mass. If thecontent of the anionic group is excessively high, such as more than 5%by mass, the water-based solid adhesive may have an excessively highviscosity to deteriorate workability and may exhibit decreased waterresistance after curing. If the content of the anionic group isexcessively low, such as less than 0.2% by mass, the resin component inthe water-based solid adhesive may not be stably dispersed.

[0150] The proportion of the alkoxysilane (A4) containing anisocyanate-reactive group is preferably such that the content of siliconatoms in the anionic-group-containing polymer (A) terminally having analkoxysilyl group is from 0.05% to 1.0% by mass, more preferably from0.1% to 0.8% by mass, and especially preferably from 0.2% to 0.6% bymass. If the silicon content is excessively high, such as more than 1.0%by mass, the water-based solid adhesive may have deteriorated stabilityand contact bonding property. If it is excessively low, such as lessthan 0.05% by mass, the water-based solid adhesive may have deterioratedadhesion.

[0151] The amount of the unsaturated carboxylic ester (A5) is preferablysuch that at least one secondary amino group is left intact in theester-modified amino-group-containing alkoxysilane (A4-5). The amountcan be selected, for example, within a range from about 0.8 to about 2moles per mole of the primary and secondary amino groups in the primaryamino group-containing alkoxysilane. The unsaturated carboxylic estercan be used in the reaction under such conditions that at least onesecondary amino group is left intact.

[0152] [Basic Compounds (B)]

[0153] The basic compounds (B) can be any of basic inorganic compoundsand basic organic compounds. Each of these basic compounds (B) can beused alone or in combination. Preferred examples of the basic inorganiccompounds are sodium hydroxide, potassium hydroxide, and other alkalimetal hydroxides; sodium carbonate, potassium carbonate, and otheralkali metal carbonates; sodium hydrogencarbonate, potassiumhydrogencarbonates, and other alkali metal hydrogencarbonates; sodiumacetate. potassium acetate, other alkali metal acetates, and otheralkali metal compounds; magnesium hydroxide, and other alkaline earthmetal hydroxides; magnesium carbonate, other alkaline earth metalcarbonates, and other alkaline earth metal compounds, as well asammonia.

[0154] Preferred examples of the basic organic compounds are aliphaticamines, aromatic amines, basic nitrogen-containing heterocycliccompounds, and other amine compounds. The aliphatic amines include, butare not limited to, trimethylamine, triethylamine, tripropylamine,triisopropylamine, tributylamine, triisobutylamine, tri-s-butylamine,tri-t-butylamine, tripentylamine, trihexylamine, and othertrialkylamines; dimethylamine, diethylamine, dibutylamine, and otherdialkylamines; methylamine, ethylamine, butylamine, and othermonoalkylamines; trimethanolamine, triethanolamine, tripropanolamine,triisopropanolamine, tributanolamine, tripentanolamine,triisopentanolamine, trihexanolamine, and other trialcoholamines;dimethanolamine, diethanolamine, and other dialcoholamines;methanolamine, ethanolamine, and other monoalcoholamines, as well asethylenediamine, and diethylenetriamine. The aromatic amines include,for example, N,N-dimethylaniline. The basic nitrogen-containingheterocyclic compounds include, but are not limited to, morpholine,piperidine, pyrrolidine, and other cyclic amines, as well as pyridine,α-picoline, β-picoline, γ-picoline, quinoline, and N-methylmorpholine.Trialkylamines, trialcoholamines, and other tertiary amine compounds arepreferred as the amine compounds.

[0155] Preferred examples of the basic compounds (B) for use in thepresent invention are sodium hydroxide, potassium hydroxide, and otheralkali metal hydroxides, ammonia, and amine compounds. Sodium hydroxide,potassium hydroxide, other alkali metal hydroxides, and other basicinorganic compounds are preferred as the basic compounds (B) when thegelling agent (D) is a salt of an aliphatic carboxylic acid, such as asodium salt and other alkali metal salts.

[0156] [Water (C)]

[0157] The water (C) for use in the present invention is notspecifically limited and can be, for example, tap water, ion exchangedwater, or pure water.

[0158] [Gelling Agents (D)]

[0159] The gelling agents (D) for use in the present invention are notspecifically limited and can be appropriately selected from knowngelling agents. Preferred examples of the gelling agents (D) are saltsof aliphatic carboxylic acids each containing 8 or more carbon atoms(“fatty acid soaps”), reaction products between sugar alcohols eachcontaining 4 or more carbon atoms and aromatic aldehydes, and salts ofreaction products of glutamic acid and other amino acids with stearicacid and other higher fatty acids (“amino acid soaps”). Each of thesegelling agents (D) can be used alone or in combination.

[0160] The aliphatic carboxylic acids each containing 8 or more carbonatoms include, but are not limited to, octanoic acid, nonanoic acid,decanoic acid, undecanoic acid, dodecanoic acid (lauric acid),tridecanoic acid, tetradecanoic acid (myristic acid), pentadecanoicacid, hexadecanoic acid (palmitic acid), heptadecaonic acid,octadecanoic acid (stearic acid), and other aliphatic saturatedmonocarboxylic acids; and oleic acid, and other aliphatic unsaturatedmonocarboxylic acids. In the present invention, aliphatic saturatedmonocarboxylic acids are preferred, of which myristic acid, stearicacid, and other aliphatic saturated monocarboxylic acids each containingabout 14 to about 18 carbon atoms are especially preferred. The salts ofthese aliphatic carboxylic acids each containing 8 or more carbon atomscan be, for example, sodium salts, potassium salts, other alkali metalsalts, and ammonium salts, of which sodium salts are preferred.Accordingly, sodium myristate and sodium stearate are optimum as thesalts of the aliphatic carboxylic acids each containing 8 or more carbonatoms.

[0161] The sugar alcohols each containing 4 or more carbon atomsinclude, but are not limited to, threitol, erythritol, and othertetritols; arabitol, ribitol, xylitol, and other pentitols; sorbitol,mannitol, iditol, talitol, galactitol (dulcitol), allitol, and otherhexitols; heptitols; octitols; nonitols; decitols; dodecitols, and othersimple sugar alcohols. Among these sugar alcohols, xylitol, sorbitol,and other sugar alcohols each containing from 5 to 7 carbon atoms arepreferred, of which sorbitol is especially preferred. The aromaticaldehydes include, but are not limited to, benzaldehyde, phthalaldehyde,isophthalaldehyde, terephthalaldehyde, carboxybenzaldehyde,nitrobenzaldehyde, cinnamaldehyde, salicylaldehyde, and anisaldehyde, ofwhich benzaldehyde is preferred. By allowing these sugar alcohols eachcontaining 4 or more carbon atoms to react with the aromatic aldehydes,benzalated products of the sugar alcohols are obtained. Among them,dibenzalated products having introduced two benzylidene groups arepreferably used. Preferred examples of the reaction products between thesugar alcohols each containing 4 or more carbon atoms and the aromaticaldehydes for use in the present invention are dibenzalated xylitol as areaction product between xylitol and benzaldehyde, and dibenzalatedsorbitol as a reaction product between sorbitol and benzaldehyde.

[0162] [Polyoxyalkylene Compounds (E)]

[0163] The polyoxyalkylene compound (E) has at least an oxyethylene unitas a constitutional unit and has an unsaturated-bond-containing organicgroup. Polyoxyalkylene glycols having at least a polyoxyethylene unitcan be advantageously used as the principal chain or main componentthereof of the polyoxyalkylene compound (E). The amount of theoxyethylene unit in the polyoxyalkylene glycol having at least thepolyoxyethylene unit can be equal to or more than 50% by mole,preferably equal to or more than 80% by mole, more preferably equal toor more than 90% by mole, and especially preferably equal to or morethan 98% by mole based on the total moles of oxyalkylene units. When theamount of the oxyethylene unit based on the total oxyalkylene units isless than 50% by mole, the polyoxyalkylene compound (E) may havedeteriorated hydrophilicity, may not stably exhibit adhesion capabilityand may not be applied with excellent workability.

[0164] Preferred examples of the unsaturated bond in theunsaturated-bond-containing organic group are carbon-carbon unsaturatedbonds such as carbon-carbon double bond and carbon-carbon triple bond,of which carbon-carbon double bond is especially preferred. Theunsaturated bond in the unsaturated-bond-containing organic group maycomprise one unsaturated bond or two or more unsaturated bonds incombination. Such unsaturated-bond-containing organic groups includemonovalent or polyvalent hydrocarbon groups having at least oneunsaturated bond. The unsaturated-bond-containing organic group may becombined with the principal chain of the polyoxyalkylene compound (E)through a divalent group. Such divalent groups include, for example,alkylene groups, cycloalkylene groups, arylene groups, and otherdivalent hydrocarbon groups, oxygen atom (—O— group), unsubstitutednitrogen atom (—NH— group), mono-substituted nitrogen atom, and carbonylgroup, and divalent groups each comprising two or more of these groups.The alkylene groups include, for example, methylene group, ethylenegroup, trimethylene group, propylene group, tetramethylene group,pentamethylene group, hexamethylene group, heptamethylene group, andoctamethylene group. The cycloalkylene groups include, for example,cyclohexylene group.

[0165] The polyoxyalkylene compound (E) for use in the present inventionpreferably has the unsaturated-bond-containing organic group at leastone of its ends (at one end or both ends). Accordingly, monovalentunsaturated-bond-containing organic groups are preferred as theunsaturated-bond-containing organic group. Among these monovalentunsaturated-bond-containing organic groups, examples of monovalentunsaturated-bond-containing hydrocarbon groups are aryl groups,cycloalkenyl groups, cycloalkadienyl groups, and vinyl group. The arylgroups include, but are not limited to, phenyl group, naphthyl group,anthryl group, phenanthryl group, and pyrenyl group, of which phenylgroup is preferred. The cycloalkenyl groups include, for example,cyclohexenyl group. The cycloalkadienyl groups include, for example,cyclohexadienyl group. These aryl groups, cycloalkenyl groups,cycloalkadienyl groups, and vinyl group may be combined with the end ofthe polyoxyalkylene compound (E) through a divalent group, as describedabove. For example, when the aryl group is combined with the end(terminal oxygen atom) of the polyoxyalkylene compound (E) through adivalent group, the aryl group combined through the divalent group mayform, for example, benzyl group, phenethyl group, and other aryl-alkylgroups; aryl-cycloalkyl groups; aryl-carbonyl groups;aryl-alkyl-carbonyl groups; and aryl-cycloalkyl-carbonyl groups. Thecycloalkenyl group or cycloalkadienyl group combined through a divalentgroup may form corresponding groups to those of the aryl group combinedthrough a divalent group. The vinyl group combined through a divalentgroup may form, for example, allyl group (2-propenyl group), isopropenylgroup, and other vinyl-alkyl groups; vinyl-phenyl group, allyl-phenylgroups, and other vinyl-(alkyl) -aryl groups; vinyl-cyclohexyl group,allyl-cyclohexyl group, and other vinyl-(alkyl)-cycloalkyl groups;(meth)acryloyl groups (acryloyl group and methacryloyl group);(meth)acryloyloxyethyl group, (meth)acryloyloxypropyl group, and other(meth)acryloyloxyalkyl groups.

[0166] The unsaturated-bond-containing organic groups also include, forexample, indenyl group, fluorenyl group, indanyl group, and otherunsaturated-bond-containing hydrocarbon groups; pyridyl group, pyrazinylgroup, pyrrolyl group, imidazolyl group, pyranyl group, furyl group,indolinyl group, isoindolinyl group, isochromanyl group, and otherunsaturated-bond-containing heterocyclic groups.

[0167] Preferred examples of the unsaturated-bond-containing organicgroups are aryl groups (especially phenyl group), aryl-alkyl groups(especially benzyl group-and other phenyl-alkyl groups), vinyl-alkylgroups (especially allyl group), and (meth)acryloyl groups. Each ofthese unsaturated-bond-containing organic groups can be used alone or incombination.

[0168] Thus, preferred polyoxyalkylene compounds (E) are polyoxyalkylenecompounds each comprising a polyoxyalkylene glycol having at least apolyoxyethylene unit and having an unsaturated-bond-containinghydrocarbon group as the unsaturated-bond-containing group introducedinto at least one of its ends. The unsaturated-bond-containinghydrocarbon group is generally combined with the terminal oxygen atom ofthe polyoxyalkylene glycol having at least a polyoxyethylene unit, wherenecessary, through another group. The unsaturated-bond-containinghydrocarbon group can therefore be introduced using a reaction in whichan oxygen atom is involved, such as etherification reaction andesterification reaction.

[0169] More specifically, examples of terminally phenylatedpolyoxyalkylene compounds each comprising a polyoxyalkylene glycolhaving at least a polyoxyethylene unit and having a phenyl groupintroduced into at least one end are polyoxyethylene monophenyl ether,polyoxyethylene monobenzyl ether, polyoxyethylene diphenyl ether,polyoxyethylene dibenzyl ether, polyoxyethylene monophenyl ethermonobenzyl ether, alkoxy-polyoxyethylene monophenyl ethers each havingone alkoxylated end, alkoxy-polyoxyethylene monobenzyl ethers eachhaving one alkoxylated end, and other polyoxyethylenes each having aphenylated end; poly(oxyethylene-oxypropylene) monophenyl ether,poly(oxyethylene-oxypropylene)monobenzyl ether,poly(oxyethylene-oxypropylene)diphenyl ether,poly(oxyethylene-oxypropylene)dibenzyl ether,poly(oxyethylene-oxypropylene)monophenyl ether monobenzyl ether,alkoxy-poly(oxyethylene-oxypropylene)monophenyl ethers each having onealkoxylated end, alkoxy-poly(oxyethylene-oxypropylene)monobenzyl etherseach having one alkoxylated end, and other oxyethylene-oxypropylenecopolymers each having a phenylated end.

[0170] Examples of terminally allylated polyoxyalkylene compounds eachcomprising a polyoxyalkylene glycol having at least apolyoxyethyleneunit and having an allyl group introduced into at least one end include,but are not limited to, polyoxyethylenemonoallyl ether, polyoxyethylenediallyl ether, alkoxy-polyoxyethylene monoallyl ethers each having onealkoxylated end, and other terminally allylated polyoxyethylenes;poly(oxyethylene-oxypropylene)monoallyl ether,poly(oxyethylene-oxypropylene)diallyl ether,alkoxy-poly(oxyethylene-oxypropylene)monoallyl ethers each having onealkoxylated end, and other terminally allylated oxyethylene-oxypropylenecopolymers.

[0171] Examples of terminally (meth)acryloylated polyoxyalkylenecompounds each comprising a polyoxyalkylene glycol having at least apolyoxyethylene unit and having a (meth) acryloyl group introduced intoat least one end include, but are not limited to, polyoxyethylenemono(meth)acrylate, polyoxyethylene di(meth)acrylate,alkoxy-polyoxyethylene mono(meth)acrylates having one alkoxylated end,and other terminally (meth)acryloylated polyoxyethylenes;poly(oxyethylene-oxypropylene)mono(meth)acrylate,poly(oxyethylene-oxypropylene)di(meth)acrylate,alkoxy-poly(oxyethylene-oxypropylene)mono(meth)acrylates each having onealkoxylated end, and other terminally (meth)acrylatedoxyethylene-oxypropylene copolymers.

[0172] Such alkoxy groups to be introduced into the end include, forexample, methoxy group, ethoxy group, propoxy group, isopropoxy group,butoxy group, and other alkoxy groups each containing about 1 to about20 carbon atoms, and preferably about 1 to about 10 carbon atoms.

[0173] The number-average molecular weight of the polyoxyalkylenecompound (E) is, for example, from 100 to 5000, preferably from 200 to5000, more preferably from 300 to 4000, and especially preferably from500 to 3000.

[0174] By using the polyoxyalkylene compound (E), the water-based solidadhesive may have further improved shape retention and slidability andcan thereby be further easily and smoothly applied. It can be applied ina further sufficient amount with further improved workability.

[0175] In particular, by using the polyoxyalkylene compound (E), thewater-based solid adhesive can exhibit higher initial adhesion (initialcohesion) and can easily and stably bond adherends with each other. Thewater-based solid adhesive has high adhesion (initial adhesion) forholding bonded adherends after the application of the water-based solidadhesive to bonding surfaces of the adherends. Accordingly, even anordinary user unsophisticated in bonding procedure can easily and stablybond the adherends using the water-based solid adhesive.

[0176] The use of the polyoxyalkylene compound (E) can also preventdrying of the water-based solid adhesive after the application and cansignificantly prolong an open time. Accordingly, by using thepolyoxyalkylene compound (E), the water-based solid adhesive can furthersatisfactorily bond adherends by contact bonding. In addition, it canyield a larger effective adhesive area in contact bonding with goodcontact bonding property. It also has excellent fitting after attachmentand exhibits good adhesion to plastics, metals and glass.

[0177] Thus, by using the polyoxyalkylene compound (E), the water-basedsolid adhesive can be applied to adherends with significantly improvedworkability and can effectively exhibit stable bonding capabilities.

[0178] The operation and advantages as described above may probably bederived from the following facts. The polyoxyalkylene compound (E) hasgood affinity with, and thereby acts as a plasticizer on, theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup. The polyoxyalkylene compound (E) is nonvolatile and hydrophilicand can thereby exhibit an activity as a humectant (moisturizing agent).In addition, it can exhibit an activity as a hardness regulator forsmoothly applying the water-based solid adhesive to a surface of anadherend upon application. Thus, the water-based solid adhesive can bondadherends under broadened conditions, and all or most of appliers(users) can allow the water-based solid adhesive to stably exhibitexcellent bonding effects.

[0179] There has been no disclosure of the use of the polyoxyalkylenecompound (E) in water-based solid adhesives, and practical utilitythereof has not been significantly known. The aforementioned operationand advantages have not been known. In addition, there has been nodisclosure of the use of the anionic-group-containing polymer (A)terminally having an alkoxysilyl group as a polymer component ofwater-based solid adhesives. Thus, the excellent operation andadvantages obtained by using the anionic-group-containing polymer (A)terminally having an alkoxysilyl group in combination with thepolyoxyalkylene compound (E) are beyond all expectations.

[0180] [Curing Accelerators (F)]

[0181] The curing accelerator (F) is represented by following Formula(1):

[0182] wherein M is one of tin atom, titanium atom, zirconium atom andbismuth atom; R¹ and R² are the same or different and are each ahydrocarbon group; R³ and R⁴ are the same or different and are each oneof a hydrogen atom and a hydrocarbon group; R⁵and R⁶ are the same ordifferent and are each a hydrogen atom or a hydrocarbon group; p is aninteger equal to or more than 1; and q is an integer from 1 to 3.

[0183] In Formula (1), M is a tin atom, titanium atom, zirconium atom orbismuth atom, of which tin atom is preferred as M.

[0184] In Formula (1), the hydrocarbon group as R¹ and R² includes, forexample, aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, andaromatic hydrocarbon groups. Such aliphatic hydrocarbon groups as R¹ andR² include, but are not limited to, methyl group, ethyl group, propylgroup, isopropyl group, butyl group, isobutyl group, t-butyl group,s-butyl group, n-pentyl group, hexyl group, heptyl group, octyl group,2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecylgroup, tridecyl group, tetradecyl group, pentadecyl group, hexadecylgroup, heptadecyl group, octadecyl group, and other alkyl groups eachcontaining 1 to 20 carbon atoms.

[0185] The alicyclic hydrocarbon groups as R¹ and R²include, but are notlimited to, cyclohexyl group, and other cycloalkyl groups eachcontaining about 5 to 10 carbon atoms in their ring, as well as groupseach having a polycyclic hydrocarbon ring such as a hydrocarbon ring innorbornane and other bridged rings. The aromatic hydrocarbon groups asR¹ and R² include, but are not limited to, phenyl group, naphthyl group,and other aryl groups.

[0186] Preferred examples of the hydrocarbon groups as R¹ and R2 arealiphatic hydrocarbon groups, of which alkyl groups each containing 1 to12 carbon atoms are more preferred, and alkyl groups each containing 1to 6 carbon atoms are especially preferred. The substituents R¹ andR²may be different but are preferably the same with each other.

[0187] The hydrocarbon group as R³ and R⁴ in Formula (1) can be thealiphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatichydrocarbon groups, and other hydrocarbon groups exemplified as thehydrocarbon groups as R¹ and R². The hydrocarbon groups as R³ and R⁴ arepreferably aliphatic hydrocarbon groups, of which alkyl groups eachcontaining about 1 to about 12, especially preferably about 1 to about6, and particularly preferably about 1 to about 4 carbon atoms are morepreferred. The substituents R³ and R⁴ may be different but arepreferably the same with each other.

[0188] The hydrocarbon group as R⁵ and R⁶ in Formula (1) can be thealiphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatichydrocarbon groups, and other hydrocarbon groups exemplified as thehydrocarbon groups as R¹ and R² or as R³ and R⁴. The hydrocarbon groupsas R⁵ and R⁶ are preferably aliphatic hydrocarbon groups, of which alkylgroups each containing about 1 to about 12, especially preferably about1 to about 6, and particularly preferably about 1 to about 4 carbonatoms are more preferred. The substituents R⁵ and R⁶ may be differentbut are preferably the same with each other.

[0189] In formula (1), p is not specifically limited, as long as it isan integer equal to or more than 1, and can be selected from integers,for example, from 1 to 10, preferably from 1 to 6, and more preferablyfrom 1 to 4.

[0190] The repetition number q is an integer from 1 to 3, preferably 2or 3, and more preferably 3. When q is 3, R⁵ and R6 are absent and threeOR³s and/or three OR⁴s are combined with silicon atom(s) in Formula (1).The repetition number q relating to OR³ and R⁵ and the repetition numberq relating to OR⁴ and R⁶ may be different but are preferably the samewith each other.

[0191] The compounds represented by Formula (1) each have hydrolyzablesilicon groups at both ends. Such hydrolyzable silicon groups include,but are not limited to, trimethoxysilyl group, triethoxysilyl group,tripropoxysilyl group, triisopropoxysilyl group, tributoxysilyl group,and other trialkoxysilyl groups; methyldimethoxysilyl group,methyldiethoxysilyl group, methyldipropoxysilyl group,methyldibutoxysilyl group, ethyldimethoxysilyl group, ethyldiethoxysilylgroup, ethyldipropoxysill group, ethyldibutoxysilyl group,propyldimethoxysilyl group, propoyldiethoxysilyl group,propyldipropoxysilyl group, propyldibutoxysilyl group, otheralkyldialkoxysilyl groups, and corresponding dialkyl(mono)alkoxysilylgroups, as well as dialkoxysilyl groups and alkoxysilyl groupscorresponding to these alkyldialkoxysilyl groups anddialkyl(mono)alkoxysilyl groups except with hydrogen atoms replacingtheir alkyl groups. The hydrolyzable silicon groups also includehydroxyl-group-containing silyl groups corresponding to thetrialkoxysilyl groups, alkyldialkoxysilyl groups, anddialkyl(mono)alkoxysilyl groups except with a hydroxyl group replacingat least one of their alkoxy groups as a result of hydrolysis.

[0192] Examples of the compounds represented by Formula (1) aredialkylstannoxane disilicate compounds andpoly(dialkylstannoxane)disilicate compounds. More specifically, examplesof the compounds represented by Formula (1) wherein M is a tin atom, R¹and R² are alkyl groups, and p is 1, namely, examples of thedialkylstannoxane disilicate compounds aredi(trialkoxysilyl-oxy)dialkyltin[dialkyltin bis(trialkoxysilicate)],di(alkyldialkoxysilyl-oxy)dialkyltin[dialkyltinbis(alkyldialkoxysilicate)], and di(dialkylalkoxysilyl-oxy)dialkyltin[dialkyltinbis(dialkylalkoxysilicate)]. Examples of the compounds represented byFormula (1) wherein M is a tin atom, R¹ and R² are alkyl groups, and pis an integer equal to or more than 2, namely, examples of thepoly(dialkylstannoxane)disilicates are poly(dialkylstannoxane) havingtrialkoxysilyl-oxy groups at both ends, poly(dialkylstannoxane) havingalkyldialkoxysilyl-oxy groups at both ends, and poly(dialkylstannoxane)having dialkylalkoxysilyl-oxy groups at both ends.

[0193] Even in the coexistence with the anionic-group-containing polymer(A) terminally having an alkoxysilyl group, the curing accelerator (F)has excellent storage stability and can prevent or inhibit curing(crosslinking) of the anionic-group-containing polymer (A) terminallyhaving an alkoxysilyl group for a long time under conditions such thatwater in a system does not decrease (for example, when the adhesive isstored in a vessel). In contrast, the water-based solid adhesive iscured (crosslinked) under such conditions that water in the systemdecreases as a result of drying due to evaporation or volatilization(for example, when the adhesive is applied to an open surface). In thiscase, the curing accelerator (F) can serve to further accelerate acuring speed. Consequently, the water-based solid adhesive of thepresent invention can have a further increased curing speed whilemaintaining excellent storage stability in spite of the use of thecuring accelerator (F).

[0194] Thus, by using the curing accelerator (F), the curing speed canbe further increased, and the time for aging (curing) or prepressing canbe shortened to thereby exhibit excellent workability. In addition, thecuring accelerator (F) does not adversely affect adhesion propertiessuch as tackiness and adhesive strength during or after curing, and thewater-based solid adhesive can thereby exhibit intrinsic excellentinitial adhesion such as initial tackiness and initial adhesivestrength. Thus, by using the curing accelerator (F), the water-basedsolid adhesive can be further easily and stably used in bonding,coating, and other procedures.

[0195] The curing accelerator (F) does not adversely affect heatresistance and water resistance of the water-based solid adhesive aftercuring. The water-based solid adhesive thereby has excellent heatresistance and water resistance after curing even when the curingaccelerator (F) is used.

[0196] There has been no disclosure of the use of the curing accelerator(F) in water-based solid adhesives that are cured as a result ofdecrease of water in the system, and practical utility thereof has notbeen substantially known. Thus, the aforementioned operation andadvantages have not been known. In addition, there has been nodisclosure of the use of the anionic-group-containing polymer (A)terminally having an alkoxysilyl group as a polymer component ofwater-based solid adhesives. Thus, the excellent operation andadvantages obtained by using the anionic-group-containing polymer (A)terminally having an alkoxysilyl group in combination with the curingaccelerator (F) are beyond all expectations.

[0197] [Water-based Solid Adhesives]

[0198] The water-based solid adhesives of the present invention eachcomprise the anionic-group-containing polymer (A) terminally having analkoxysilyl group, the basic compound (B), the water (C), the gellingagent (D), and the polyoxyalkylene compound (E) and/or the curingaccelerator (F) added according to necessity and are self-curable. Insuch self-curable water-based solid adhesives (herein after may besimply referred to as “water-based solid adhesive(s)”), it is preferredthat a water-based resin composition is gelled by the gelling agent (D),which water-based resin composition comprises theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup, the basic compound (B), and the water (C), and where necessarythe polyoxyalkylene compound (E) and/or the curing accelerator (F). Thewater-based resin composition can be a mixture of theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup, the basic compound (B) and the water (C), and where necessary thepolyoxyalkylene compound (E) and/or the curing accelerator (F).Alternatively, the water-based resin composition can be a reactioncomposition containing a reaction product of theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup with the basic compound (B) and the water (C) as a result of themixing. Such a reaction of the anionic-group-containing polymer (A)terminally having an alkoxysilyl group with the basic compound (B)includes a neutralization reaction in which the anionic group in theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup is partially or fully neutralized with the basic compound (B).Namely, the anionic group in the anionic-group-containing polymer (A)terminally having an alkoxysilyl group forms a salt as a result of thereaction between the anionic-group-containing polymer (A) terminallyhaving an alkoxysilyl group and the basic compound (B).

[0199] The reaction of the anionic-group-containing polymer (A)terminally having an alkoxysilyl group with the water (C) includes, forexample, a hydrolysis reaction in which the alkoxysilyl group at the endof the anionic-group-containing polymer (A) terminally having analkoxysilyl group is hydrolyzed with the water (C). Namely, the terminalalkoxysilyl group of the anionic-group-containing polymer (A) terminallyhaving an alkoxysilyl group is partially or fully converted into asilanol group and/or a siloxane bond as a result of the reaction betweenthe anionic-group-containing polymer (A) terminally having analkoxysilyl group and the water (C). In other words, at least onealkoxysilyl group among the terminal alkoxysilyl groups in theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup is affected by the hydrolysis reaction with the water (C). Theterm “silanol group” as used herein means a group comprising a siliconatom having at least one hydroxyl group, and the silanol group may havea substituent such as an alkoxy group.

[0200] The reaction products as a result of the reaction of theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup with the basic compound (B) and the water (C) include, forexample, water-based silanolated polymers in which the anionic group inthe anionic-group-containing polymer (A) terminally having analkoxysilyl group is neutralized with the basic compound (B) to form asalt of the anionic group, and the terminal alkoxysilyl groups arepartially or fully hydrolyzed with the water (C) to form a silanol groupand/or a siloxane bond. In the water-based solid adhesives of thepresent invention, it is preferred that a water-based resin compositionis gelled by the gelling agent (D), which water-based resin compositionhas an anionic group neutralized with the basic compound (B) and aterminal alkoxysilyl group hydrolyzed with the water (C) in theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup.

[0201] The water-based solid adhesives can be prepared by mixing theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup, the basic compound (B), the water (C), and the gelling agent (D),where necessary with the polyoxyalkylene compound (E) and/or the curingaccelerator (F). The order of mixing these components is notspecifically limited. For example, the water-based solid adhesives canbe prepared in the following manner. Initially, the basic compound. (B)and the water (C), and where necessary the polyoxyalkylene compound (E)are added to the anionic-group-containing polymer (A) terminally havingan alkoxysilyl group, the resulting mixture is preferably vigorouslystirred for accelerating the neutralization reaction, hydrolysisreaction, and other reactions to thereby yield an aqueous solution or anaqueous dispersion. Where necessary, the aqueous solution or aqueousdispersion is further treated with the curing accelerator (F) withstirring, and the resulting mixture is gelled with the gelling agent (D)and, if required, treated with a defoaming agent and other additives by,for example, mixing with stirring to thereby yield a water-based solidadhesive. The resulting adhesive is a water-based solid adhesive and themolding method for molding it into a specific shape is not specificallylimited. For example, the water-based solid adhesive can be molded intoa specific shape by placing the adhesive before solidification in avessel or mold for molding into a specific shape or by molding thewater-based solid adhesive after solidification into a specific shape.

[0202] The basic compound (B) can be used in the preparation of theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup. For example, the basic compound (B) may be added in a reaction ofthe alkoxysilane (A4) containing an isocyanate-reactive group with thereaction product of the isocyanate-reactive compound (A1), theisocyanate-reactive compound (A2), and the polyisocyanate (A3). Thus,the reaction can be performed in the presence of the basic compound (B).

[0203] The amount of the basic compound (B) can be selected within arange from about 50% to about 120% by mole, and preferably from about80% to about 110% by mole relative to the anionic group in theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup.

[0204] The amount of the water (C) can be selected within a range ofabout 65 to about 900 parts by mass, and preferably about 100 to about400 parts by mass relative to 100 parts by mass of theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup.

[0205] The amount of the gelling agent (D) can be selected within arange from about 0.02 to about 100 parts by mass, and preferably fromabout 5 to about 80 parts by mass relative to 100 parts by mass of theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup. If the amount of the gelling agent (D) is excessively small, thewater-based solid adhesive may be difficult to solidify. If it isexcessively large, the water-based solid adhesive may have deterioratedadhesion.

[0206] The amount of the polyoxyalkylene compound (E), if any, can beselected within a range from about 0.1 to about 50 parts by mass,preferably from about 1 to about 30 parts by mass, and more preferablyfrom about 5 to about 25 parts by mass relative to 100 parts by mass ofthe anionic-group-containing polymer (A) terminally having analkoxysilyl group.

[0207] The amount of the curing accelerator (F), if any, can be selectedwithin a range from about 0.01 to about 2 parts by mass, and preferablyfrom about 0.05 to about 1 part by mass relative to 100 parts by mass ofthe anionic-group-containing polymer (A) terminally having analkoxysilyl group.

[0208] In the water-based solid adhesives of the present invention, thehydroxyl value (OHV) of the water-based resin composition before gellingis not specifically limited and can be selected within a range of, forexample, about 60 to about 400 mg-KOH/g, and preferably about 80 toabout 350 mg-KOH/g. The water-based resin composition before gelling isthe water-based resin composition comprising theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup, the basic compound (B) and the water (C) with, where necessary,the polyoxyalkylene compound (E) and/or the curing accelerator (F). Theneutralization ratio of the anionic group such as carboxyl group is notspecifically limited and is preferably, for example, equal to or morethan 80% and more preferably 90% to 100%. The resin content is notspecifically limited and can be selected within a range from about 10%to about 60% by mass, and preferably from about 20% to about 50% bymass.

[0209] The water-based solid adhesives of the present invention can becompletely water-based solid adhesives free of organic solvents. Namely,the water-based solid adhesives of the present invention can be free oforganic solvents, although the fact is that conventionally commerciallyavailable water-based solid adhesives contain a small amount of organicsolvents. The water-based solid adhesives of the present invention mayfurther comprise a hydrophilic organic solvent (water-soluble organicsolvent) such as ketones and lower alcohols for adjusting the viscosityof their aqueous solution or aqueous dispersion. Each of these organicsolvents can be used alone or in combination. Examples of the ketonesinclude acetone. Examples of the lower alcohols are methanol, ethanol,propanol, isopropanol, butanol, isobutanol, s-butanol, t-butanol,pentanol, hexanol, and other monohydric alcohols; ethylene glycol,propylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol,1,6-hexanediol, glycerol, and other polyhydric alcohols. Thewater-soluble organic solvents also include propylene carbonate;dimethyl carbonate; trimethyl phosphate; diethers, diesters, and diallylethers of polyoxyethylene; diethers and diacetates of glycols;1,3-dioxolane; and N-methyl-2-pyrrolidone. The amount of the organicsolvents can be appropriately set depending on, for example, themagnitude of the viscosity to be adjusted and can be selected within arange, for example, from about 0 to about 100 parts by mass, andpreferably from about 1 to about 50 parts by mass relative to 100 partsby mass of the anionic-group-containing polymer (A) terminally having analkoxysilyl group.

[0210] The water-based solid adhesives may further comprise ahydrophilic solvent for improving or modifying wettability. Suchhydrophilic solvents for improving wettability are not specificallylimited and include, for example, N-methyl-2-pyrrolidone,polyoxyethylene alkyl ethers, and other surfactants, as well as sodiumalginate, mucopolysaccharides, and sodium acrylate.

[0211] The water-based solid adhesives of the present invention mayfurther comprise a humectant. By using the humectant, the water-basedsolid adhesives may have improved coating performance. Such humectantsare not specifically limited and can be any of known or conventionalhumectants. Examples of the humectants are ethylene glycol, polyethyleneglycols each having a number-average molecular weight of less than orequal to 400, ethylene glycol monoethyl ether and other Cellosolves, aswell as diethylene glycol monoethyl ether and other carbitols, and otherethylene glycol derivatives; propylene glycol, propylene glycolmonomethyl ether, and other propylene glycol derivatives; glycerol,1,3-butanediol, and other polyhydric alcohols; sorbitol, and otherpolysaccharides; monoethanolamine, diethanolamine, triethanolamine, andother alkanolamines; and 1,3-dimethyl-2-imidazolidinone.

[0212] The water-based solid adhesives of the present invention mayfurther comprise any of additives, other additional components andsolvents. Such additives, additional components and solvents include,for example, defoaming agents, fillers, plasticizers, age resistors,ultraviolet absorbers, antioxidants, heat stabilizers, coloring agentssuch as pigments and dyes, antimolds (fungicides), wetting accelerators,viscosity improvers, perfumes, tackifiers such as emulsion tackifiers,coupling agents such as titanate coupling agents, aluminum couplingagents, and silane coupling agents, photo-curing catalysts, emulsifiers,surfactants, emulsions and latices, crosslinking agents, andwater-soluble polymers. The fillers include, but are not limited to,calcium carbonate, treated calcium carbonates, fumed silica, clay, talc,balloons, Neuburg silica, kaolin, and aluminum silicate. Theplasticizers include, but are not limited to, dioctylphthalate, dibutylphthalate, and other phthalic esters; dioctyl adipate, dibutyl sebacate,and other aliphatic carboxylic esters. The tackifiers include, but arenot limited to, stabilized rosin esters, polymerized rosin esters,terpene phenol, petroleum resins, and other emulsion tackifiers. Thecrosslinking agents include, for example, isocyanate crosslinkingagents, epoxy crosslinking agents, carbodiimide crosslinking agents,aziridine crosslinking agents, polyethyleneimine crosslinking agents,melamine crosslinking agents, and colloidal silica. The solvents for usein the present invention are not specifically limited as long as theyare miscible or compatible with the anionic-group-containing polymer (A)terminally having an alkoxysilyl group, the basic compound (B), thewater (C), the gelling agent (D), and other components.

[0213] As described above, the water-based solid adhesives of thepresent invention comprise, as an adhesive component polymer, theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup, which comprises an anionic-group-containing polymer having an endalkoxysilylated by the alkoxysilane compound (A4) containing anisocyanate-reactive group. The anionic-group-containing polymer (A)terminally having an alkoxysilyl group forms a water-based silanolatedpolymer with the basic compound (B) and the water (C) in the water-basedsolid adhesives. Accordingly, when the water-based solid adhesive isapplied and water therein decreases by evaporation, the silanol group ofthe water-based silanolated polymer in the water-based solid adhesiveundergoes a condensation reaction and the water-based solid adhesive iscured (crosslinked). Specifically, the adhesive component polymer in thewater-based solid adhesives of the present invention has reactivity andreacts to cure and crosslink to thereby exhibit adhesion. Namely, thewater-based solid adhesives of the present invention are self-curablewater-based solid adhesives. In contrast, adhesive component polymers inconventional water-based solid adhesives do not react in curing butsolidify by evaporation of water to thereby exhibit adhesion.

[0214] The adhesive component polymer in the present invention has askeleton having a urethane bond but its end is alkoxysilylated with thealkoxysilane compound (A4) containing a primary or secondary amino groupand thereby has condensation reactivity due to silanol group. Thepolymer is not a regular polyurethane but is an anionic-group-containingpolymer terminally having analkoxysilyl group. The adhesive componentpolymer in the water-based solid adhesives of the present invention isnot only different in structure but also significantly different inmechanism for exhibiting adhesion and in operation and advantages due tothe polymer structure from the adhesive component polymers inconventional water-based solid adhesives as will be described in detaillater.

[0215] The condensation reaction of the silanol group of thewater-soluble silanolated polymer in the water-based solid adhesives ofthe present invention plays a major role in curing, and the water-basedsolid adhesives have a curing speed less dependent on the drying speedof water and have a higher initial adhesive strength than conventionalequivalents. The crosslinking reaction proceeds with a decreasing waterand can proceed even in the presence of water to some extent, and thewater-based solid adhesives can thereby exhibit cohesion even when theycontain some water.

[0216] An ion center (a salt of the anionic group, such as a carboxylicacid salt) is introduced into the molecule of the water-basedsilanolated polymer for making it water-borne and plays a role as anaccelerating catalyst of the condensation reaction between the silanolgroups. This may also be involved in the higher curing speed and higherinitial adhesive strength of the water-based solid adhesives.

[0217] Thus, the-water-based solid adhesives of the present inventionhave high initial adhesive strength, can thereby bond adherends withoutprepressing or with prepressing in a shorter time with good workabilityand can easily bond plural adherends. In particular, they have excellentinitial adhesive strength even when they are free of organic solventsand are completely water-based.

[0218] In addition, the anionic-group-containing polymer (A) terminallyhaving an alkoxysilyl group serving as an adhesive component polymer inthe water-based solid adhesives of the present invention can be apolymer having a relatively low molecular weight. For example, itsnumber-average molecular weight can be selected within a range fromabout 3000 to 50000 and preferably from about 10000 to 30000. Theanionic-group-containing polymer (A) forms a polymer having a highermolecular weight due to formed siloxane bonds after curing.

[0219] The water-based solid adhesives of the present invention canfurther satisfactorily bond adherends by contact bonding by using theisocyanate-reactive compound (A1-1) having a number-average molecularweight of equal to or more than 500 and the isocyanate-reactive compound(A1-2) having a number-average molecular weight less than 500 incombination as the isocyanate-reactive compound (A1). In addition, byusing the polyol compound (A1-2) as the isocyanate-reactive compound(A1-2), they can much further satisfactorily bond adherends by contactbonding.

[0220] The water-based solid adhesives of the present invention can havefurther improved initial adhesive strength, namely can be fast-curewater-based solid adhesives by using the isocyanate-reactive compound(A1-1) having a number-average molecular weight of equal to or more than500 and the isocyanate-reactive compound (A1-2) having a number-averagemolecular weight less than 500 in combination as the isocyanate-reactivecompound (A1) and using the polyamine compound (A1-2) containing noanionic group and having a number-average molecular weight less than 500as the isocyanate-reactive compound (A1-2) having a number-averagemolecular weight less than 500.

[0221] In contrast to conventional water-based solid adhesives, thewater-based solid adhesives of the present invention can bond adherendsby contact bonding, can be used as contact-bonding stick adhesives(contact type stick adhesives) and can bond nonporous articles with eachother by appropriately selecting the isocyanate-reactive compound(s)(A1). They can also have further higher initial adhesive strength thanconventional water-based solid adhesives, can be used as fast cure typestick adhesives (fast cure stick adhesives) and can bond nonporousadherends with each other by appropriately selecting theisocyanate-reactive compound(s) (A1), namely by using the polyaminecompound (A1-2).

[0222] By using the polyoxyalkylene compound (E) and/or the curingaccelerator (F), the operation and advantages of these compounds can beeffectively exhibited, and the resulting water-based solid adhesivesbecome more excellent. For example, by using the polyoxyalkylenecompound (E), the water-based solid adhesives can have further improvedinitial adhesive strength and can thereby further easily and stably bondadherends with each other. Accordingly, even ordinary usersunsophisticated in bonding procedure can easily and stably bond theadherends using the water-based solid adhesives without misoperation. Byusing the curing accelerator (F), the water-based solid adhesives can becured in a further higher speed and become further excellent fast curestick adhesives.

[0223] When the anionic-group-containing polymer (A) terminally havingan alkoxysilyl group has a number-average molecular weight on the orderof several tens of thousands, the water-based resin compositioncomprising the anionic-group-containing polymer (A) terminally having analkoxysilyl group, the basic compound (B), and the water (C), wherenecessary with the polyoxyalkylene compound (E) and/or the curingaccelerator (F) is prepared as an aqueous solution or a colloidaldispersion and can thereby be advantageously molded into a stickadhesive by using the gelling agent (D).

[0224] The polymer serving as an adhesive component in the water-basedsolid adhesives of the present invention forms a crosslinked structureand becomes reticulate as a result of curing. The adhesive after curingthereby exhibits excellent water resistance and heat resistance. Inother words, the water-based or aqueous polymer exhibits high adhesionand has excellent water resistance and heat resistance after curing.

[0225] In addition, the water-based solid adhesives of the presentinvention each have the polymer serving as an adhesive component andhaving a silanol group and can thereby exhibit good adhesion not only topaper and other porous materials but also to metals, glass, and othernonporous materials. Adherends to be bonded using the water-based solidadhesives of the present invention are not specifically limited andinclude various adherends as described later.

[0226] The reason why the silanol groups of the water-based silanolatedpolymer in the water-based solid adhesives of the present inventionremain stable in spite of containing water is not clarified but isprobably as follows. For example, the silanol groups are protected by alarge amount of water molecules in the system to thereby prevent orinhibit the condensation reaction between the silanol groups.Alternatively or in addition, the silanol groups are protected by asubstituent combined with the nitrogen atom of a secondary amino groupor tertiary amino group derived from the amino-group-containingalkoxysilane (A4-1) serving as the alkoxysilane compound (A4) containingan isocyanate-reactive group to thereby prevent or inhibit thecondensation reaction between the silanol groups. The substituent justmentioned above is, for example, a long chain substituent, or an estermoiety thereof, derived from the unsaturated carboxylic ester (A5).Thus, the water-based solid adhesives of the present invention haveexcellent stability and exhibit a high curing speed despite that theyare one-part crosslinking water-based adhesives.

[0227] In addition, the water-based solid adhesives are waterborne, canbe completely waterborne free of organic solvents and thereby haveexcellent handleability and high safety to humans and the environment.

[0228] Particularly, the water-based solid adhesives of the presentinvention can keep their shapes satisfactorily, are thereby resistant tobreaking in application and are prevented from breaking duringapplication. They also have good slidability and are thereby easilyapplied to adherends, for example, by coating. They can be cured withoutheating and can be cured even at room temperature.

[0229] The water-based solid adhesives of the present invention aretherefore very useful as contact bonding type or fact curing type stickadhesives, and other stick adhesives.

[0230] The anionic-group-containing polymers represented by Formula (2)each terminally having analkoxysilyl group, wherein X in Formula (2) isthe alkoxysilyl-containing group represented by any of Formulae (2b),(2c), and (2d), can be used as polymer components of not only suchwater-based solid adhesives, but also of water-based adhesives otherthan water-based solid adhesives, water-based coating compositions suchas water-based paints, as well as binders, laminates, sealers, primers,sizing agents, and sealants. Among them, anionic-group-containingpolymers represented by Formula (2) each terminally having analkoxysilylgroup, where in X in Formula (2) is the alkoxysilyl-containing grouprepresented by any of Formulae (2c) and (2d), are especially preferredas such polymer components. These polymers can be prepared as solidcompositions such as water-based solid adhesives by using the gellingagent (D). Alternatively, when the gelling agent (D) is not used, thepolymers can be prepared as liquid compositions such as one-partwater-based adhesives and water-based coating agents, and otherwater-based liquid adhesives. Naturally, they can be prepared as contactbonding type or fast curing type water-based compositions byappropriately selecting the isocyanate-reactive compound(s) (A1) andother components.

[0231] When the water-based solid adhesives of the present invention arecontact bond adhesives, they can bond adherends by contact bonding. Whenthe water-based solid adhesives are fast cure adhesives and otheradhesives than contact bond adhesives, they can bond adherends byregular bonding and can be cured fast. The water-based adhesivesprepared without the use of the gelling agent (D) can also bondadherends by contact bonding or regular bonding. In the bondingprocedure, various adherends can be used.

[0232] Such adherends to be bonded using the water-based solid adhesivesof the present invention are not specifically limited, can be any ofporous materials and nonporous materials and can be selected from amonga wide variety of materials. More specifically, the materials for suchadherends include, but are not limited to, wood, plywood, chipboards,particle boards, hard boards, and other woody materials; slates, calciumsilicate boards, mortar, tiles, and other inorganic materials; melamineresin overlaid boards, Bakelite boards, foaming polystyrene, films andmolded articles of plastics, such as poly(vinyl chloride) films andmolded articles, polyester films and molded articles, and polystyrenefilms and molded articles, and other plastic materials;naturally-occurring rubbers, synthetic rubbers, silicone rubbers, andother rubber materials; corrugated cardboard, paper boards, kraft paper,and other paper materials, as well as moisture-proof paper, othersurface treated converted paper, other converted paper, and other papermaterials that are difficult to bond, glass materials, metallicmaterials such as iron, aluminum, stainless steel, and copper, leathermaterials, fabrics, non-woven fabrics, and other fibrous materials.Conventional stick adhesives have been virtually applied to paper andother adherends of porous materials. In contrast, the water-based solidadhesives of the present invention can be applied to adherendscomprising a wide variety of materials and can also be applied tobonding of nonporous materials with each other by contact bonding.

[0233] The adherends can be adherends comprising the same material ormay be adherends comprising different materials. Each of these adherendscan be used alone or in combination.

[0234] Thus, the water-based solid adhesives of the present inventioncan be advantageously used as, for example, wood-paper water-based solidadhesives for bonding wood products comprising woody materials or paperproducts comprising paper materials or paper materials that aredifficult to bond, of which water-based solid adhesives forschoolchildren are preferred; leather-plastic water-based solidadhesives for bonding leather products comprising leather materials orplastic products comprising plastic materials, of which water-basedsolid adhesives for use in hobbies are preferred; fiber water-basedsolid adhesives for bonding fibrous materials; household water-basedsolid adhesives for use in a wide variety of applications at home, ofwhich water-based solid adhesives for repairing furniture are preferred;industrial water-based solid adhesives for bonding plastic boards,foaming polystyrene, plywood, wallpapers, upholstery, and othermaterials.

[0235] The water-based solid adhesives of the present invention can beused in various bonding procedures such as a process in which adherendsare bonded with each other immediately after the application of thewater-based solid adhesive to the adherends, and a contact bondingprocess in which adherends are bonded with each other when thewater-based solid adhesive exhibits cohesion (tackiness) after a settime period from the application of the water-based solid adhesive tothe adherends. The water-based solid adhesives can bond adherends bycontact bonding despite that they are water-based solid adhesives.Contact bonding processes for use in the present invention include aprocess as described in Japanese Industrial Standards (JIS) K 6800 inwhich the adhesive in question is applied to two bonding faces of twoadherends to be bonded, and the two adherends are affixed or attachedwhen the adhesive exhibits its tackiness after a lapse of a set timeperiod, as well as a process in which the adhesive is applied to oneface of one of two adherends to be bonded, and the two adherends areaffixed when the adhesive exhibits its tackiness after a lapse of a settime period. The term “contact bonding” as used herein means a procedurein which the adhesive is applied to a bonding face of at least one oftwo adherends to be bonded, and the two adherends are affixed orattached when the adhesive exhibits its tackiness after a lapse of a settime period.

[0236] As is described above, the water-based solid adhesives of thepresent invention can be applied with good workability, have excellentfitting after attachment of adherends, have good adhesion to plastics,metals, and glass and exhibit excellent heat resistance and waterresistance after curing. They also have high safety to humans and theenvironment. They can keep their shapes satisfactorily, have excellentslidability and can thereby be easily applied. In addition, they canbond adherends by contact bonding despite that they are water-basedsolid adhesives. Accordingly, the water-based solid adhesives of thepresent invention are very useful as stick adhesives.

EXAMPLES

[0237] The present invention will be illustrated in further detail withreference to several examples below, which are not intended to limit thescope of the invention. All parts and percentages are by mass unlessotherwise specified. Materials used in the examples and comparativeexamples are as follows.

[0238] [Compounds Containing No Anionic Group and Having PluralIsocyanate-Reactive Groups]

[0239] (1) Trade name “PTMG 2000” [a polytetramethylene ether glycolavailable from Mitsubishi Chemical Corporation, number-average molecularweight: 2000, hydroxyl value: 56.1 mg-KOH/g; hereinafter may be referredto as “isocyanate-reactive compound (A1-a)”]

[0240] (2) Trade name “NS 2471” [a polyester diol available from AsahiDenka Co., Ltd., number-average molecular weight: 2000, hydroxyl value:56.1 mg-KOH/g; hereinafter may be referred to as “isocyanate-reactivecompound (A1-b)”]

[0241] (3) Trade name “PLACCEL 220EC” [a polycarbonate diol availablefrom Daicel Chemical Industries, Ltd., number-average molecular weight:2000,.hydroxyl value: 56.1 mg-KOH/g; hereinafter may be referred to as“isocyanate-reactive compound (A1-c)”]

[0242] (4) 1,4-Butanediol [hereinafter may be referred to as“isocyanate-reactive compound (A1-d)”]

[0243] (5) Ethylenediamine [hereinafter may be referred to as“isocyanate-reactive compound (A1-e)”]

[0244] [Compound Having an Anionic Group and Plural Isocyanate-ReactiveGroups]

[0245] (1) 2,2-Dimethylolbutanoic acid [hydroxyl value: 758.1 mg-KOH/g;hereinafter may be referred to as “isocyanate-reactive compound (A2-1)”]

[0246] [Polyisocyanate Compound]

[0247] (1) Isophorone diisocyanate [isocyanate content (NCO content):37.8%, IPDI; hereinafter may be referred to as “polyisocyanate (A3-1)”]

[0248] [Alkoxysilane Compounds Containing Isocyanate-Reactive Group]

[0249] (1) Trade name “KBM 602”[N-β(aminoethyl)-γ-aminopropylmethyldimethoxysilane available fromShin-Etsu Chemical Co., Ltd.; hereinafter may be referred to as“amino-group-containing alkoxysilane (A4-1)”]

[0250] (2) Trade name “KBM 603”(N-β(aminoethyl)-γ-aminopropyltrimethoxysilane available from Shin-EtsuChemical Co., Ltd.; hereinafter may be referred to as“amino-group-containing alkoxysilane (A4-2)”]

[0251] (3) Trade name “KBM 903” [γ-aminopropyltrimethoxysilane availablefrom Shin-Etsu Chemical Co., Ltd.; hereinafter may be referred to as“amino-group-containing alkoxysilane (A4-3)”]

[0252] (4) Trade name “KBM 573” [N-phenyl-γ-aminopropyltrimethoxysilaneavailable from Shin-Etsu Chemical Co., Ltd.; hereinafter may be referredto as “amino-group-containing alkoxysilane (A4-4)”]

[0253] (5) Trade name “KBM 803” [γ-mercaptopropyltrimethoxysilaneavailable from Shin-Etsu Chemical Co., Ltd.; hereinafter may be referredto as “amino-group-containing alkoxysilane (A4-5)”]

[0254] [Unsaturated Carboxylic Ester]

[0255] (1) 2-Ethylhexyl acrylate [hereinafter may be referred to as“carboxylic ester (A5-1)”]

[0256] [Basic Compound]

[0257] (1) Sodium hydroxide

[0258] [Water]

[0259] (1) Ion-exchanged water (deionized water)

[0260] [Gelling Agent]

[0261] (1) Sodium stearate

[0262] [Polyoxyalkylene Compounds having an Unsaturated-Bond-ContainingOrganic Group and at Least an Oxyethylene Unit, and Other HydrophilicCompounds]

[0263] (1) Polyethylene glycol having a phenylated end and having anumber-average molecular weight of 500 (hereinafter may be referred toas “hydrophilic compound (1)”)

[0264] (2) Polyethylene glycol having a phenylated end and having anumber-average molecular weight of 100 (hereinafter may be referred toas “hydrophilic compound (2)”)

[0265] (3) Polyethylene glycol having a phenylated end and having anumber-average molecular weight of 2000 (hereinafter may be referred toas “hydrophilic compound (3)”)

[0266] Infrared absorption spectra (IR) of the hydrophilic compound (1)[the polyethylene glycol having a phenylated end and having anumber-average molecular weight of 500] and a polyethylene glycol havinga number-average molecular weight of 500 were determined at roomtemperature using a KBr plate. The resulting infrared absorptionspectral data are shown in FIGS. 1 and 2, respectively. FIGS. 1 and 2are graphs showing the infrared absorption spectral data of thehydrophilic compound (1) (the polyethylene glycol having a phenylatedend) and of the polyethylene glycol having a number-average molecularweight of 500, respectively. FIG. 3 is a graph showing thesuperimposition of the infrared absorption spectral data of FIG. 1 andthe infrared absorption spectral data of FIG. 2. FIGS. 1, 2, and 3 showthat the polyethylene glycol having a phenylated end can be clearlydistinguished from the regular polyethylene glycol in the infraredabsorption spectra.

[0267] In addition, ¹H-nuclear magnetic resonance spectra (NMR) of thehydrophilic compound (1) [the polyethylene glycol having a phenylatedend and having a number-average molecular weight of 500] and thepolyethylene glycol having a number-average molecular weight of 500 weredetermined. The resulting ¹H-nuclear magnetic resonance spectral dataare shown in FIGS. 4 and 5, respectively. FIGS. 4 and 5 are graphsshowing the ¹H-nuclear magnetic resonance spectral data of thehydrophilic compound (1) (the polyethylene glycol having a phenylatedend) and of the polyethylene glycol having a number-average molecularweight of 500, respectively. FIGS. 4 and 5 show that the polyethyleneglycol having a phenylated end can also be clearly distinguished fromthe regular polyethylene glycol in the ¹H-nuclear magnetic resonancespectra.

[0268] Accordingly, the hydrophilic compounds (1), (2) and (3) each havean unsaturated-bond-containing organic group and at least an oxyethyleneunit and fall into the polyoxyalkylene compounds (E). The hydrophiliccompounds (1), (2) and (3) are polyethylene glycols having a phenylatedend obtained by introducing a phenyl group or benzyl group into the endof a polyethylene glycol.

[0269] [Curing Accelerators]

[0270] (1) Trade name “NEOSTANN U-303” [dibutyltinbis(triethoxysilicate); (n-C₄H₉)₂Sn[OSi(OC₂H₅)₃]₂, available from NittoKasei Co., Ltd.; hereinafter may be referred to as “curing accelerator(1)”]

[0271] (2) Trade name “NEOSTANN U-700”[bis(dibutylstannoxane)bis(triethoxysilicate);{[(C₂H₅O)₃SiO](n-C₄H₉)₂Sn}₂O, available from Nitto Kasei Co., Ltd.;herein after maybe referred to as “curing accelerator (2)”]

Preparation Example 1

[0272] The carboxylic ester (A5-1) was mixed with theamino-group-containing alkoxysilane (A4-1) in a ratio of the former tothe later of 2:1 by mole, the resulting mixture was allowed to react at50° C. for 7 days and thereby yielded a reaction product (hereinaftermay be referred to as “amino-group-containing alkoxysilane (A4-a)”).

Preparation Example 2

[0273] The carboxylic ester (A5-1) was mixed with theamino-group-containing alkoxysilane (A4-2) in a ratio of the former tothe later of 2:1 by mole, the resulting mixture was allowed to react at50° C. for 7 days and thereby yielded a reaction product (hereinaftermay be referred to as “amino-group-containing alkoxysilane (A4-b)”).

Preparation Example 3

[0274] The carboxylic ester (A5-1) was mixed with theamino-group-containing alkoxysilane (A4-3) in a ratio of the former tothe later of 1:1 by mole, the resulting mixture was allowed to react at50° C. for 7 days and thereby yielded a reaction product (hereinaftermay be referred to as “amino-group-containing alkoxysilane (A4-c)”).

Example 1

[0275] In a four-neck separable flask equipped with a stirrer, anitrogen supply tube, a thermometer, and a condenser, 100 parts of theisocyanate-reactive compound (A1-a), 16.7 parts of theisocyanate-reactive compound (A2-1), 57 parts of the polyisocyanate(A3-1), 7.7 parts of the isocyanate-reactive compound (A1-d), and 40parts of acetone were placed and were allowed to react at a temperatureof 75° C. to 80° C. under the flow of nitrogen gas for 3 hours andthereby yielded are action mixture containing acarboxyl-group-containing polymer terminally having an isocyanate groupand containing 0.4% of residual isocyanate group.

[0276] All of the reaction mixture containing thecarboxyl-group-containing polymer terminally having an isocyanate groupwas further treated with 10 parts of the amino-group-containingalkoxysilane (A4-a) at a temperature of 75° C. to 80° C. under the flowof nitrogen gas for 1 hour and thereby yielded a reaction mixturecontaining a carboxyl-group-containing polymer terminally having analkoxysilyl group.

[0277] Next, the reaction mixture containing thecarboxyl-group-containing polymer terminally having an alkoxysilyl groupwas cooled to 40° C. and was then added to an aqueous solutioncontaining 4.5 parts of sodium hydroxide in 294 parts of deionized waterwith stirring at a high speed and thereby yielded a dispersion. Acetonewas then removed from the dispersion by distillation at 45° C. to 50° C.under reduced pressure, the resulting dispersion was adjusted to a solidcontent of 40% with deionized water and thereby yielded a water-basedsilanolated resin composition.

[0278] In a flask in a thermostatic bath at 80° C., 100 parts of thewater-based silanolated resin composition (stock composition) and 7parts of sodium stearate were placed with stirring, the resultingmixture was then taken out from the flask 1 hour later, was placed in astick-shaped case without delay, was left stand to cool and therebyyielded a stick adhesive.

Examples 2 to 9

[0279] Stick adhesives according to Examples 2 to 9 were prepared by theprocedure of Example 1, except that they have compositions shown inTables 1 and 2.

Example 10

[0280] In a four-neck separable flask equipped with a stirrer, anitrogen supply tube, a thermometer, and a condenser, 100 parts of theisocyanate-reactive compound (A1-b), 6.0 parts of theisocyanate-reactive compound (A1-d), 16.7 parts of theisocyanate-reactive compound (A2-1), 60.6 parts of the polyisocyanate(A3-1), and 40 parts of acetone were placed and were allowed to react ata temperature of 75° C. to 80° C. under the flow of nitrogen gas for 3hours and thereby yielded a reaction mixture containing acarboxyl-group-containing polymer terminally having an isocyanate groupand containing 2.0% of residual isocyanate group.

[0281] All of the reaction mixture containing thecarboxyl-group-containing polymer terminally having an isocyanate groupwas further treated with 20.7 parts of the amino-group-containingalkoxysilane (A4-b) at a temperature of 75° C. to 80° C. under the flowof nitrogen gas for 1 hour and thereby yielded a reaction mixturecontaining a carboxyl-group-containing polymer terminally having anisocyanate group and an alkoxysilyl group.

[0282] Next, the reaction mixture containing thecarboxyl-group-containing polymer terminally having an isocyanate groupand an alkoxysilyl group was cooled to 40° C., was added to an aqueoussolution containing 4.5 parts of sodium hydroxide and 1.6 parts of theisocyanate-reactive compound (A1-e) in 313 parts of deionized water withstirring at a high speed and thereby yielded a dispersion containing acarboxyl-group-containing polymer terminally having an alkoxysilylgroup, whose carboxyl group may be in the form of a salt. Acetone wasthen removed from the dispersion by distillation at 45° C. to 50° C.under reduced pressure, the resulting dispersion was adjusted to a solidcontent of 40% with deionized water and thereby yielded a water-basedsilanolated resin composition.

[0283] In a flask in a thermostatic bath at 80° C., 100 parts of thewater-based silanolated resin composition (stock composition) and 7parts of sodium stearate were placed with stirring, the resultingmixture was then taken out from the flask 1 hour later, was placed in astick-shaped case without delay, was left stand to cool and therebyyielded a stick adhesive.

Example 11

[0284] A water-based silanolated resin composition was prepared by theprocedure of Example 1. In a flask in a thermostatic bath at 80° C., 100parts of the water-based silanolated resin composition (stockcomposition, solid content 40%), 7 parts of sodium stearate, and 1.0part of the hydrophilic compound (1) were placed with stirring, theresulting mixture was then taken out from the flask 1 hour later, wasplaced in a stick-shaped case without delay, was left stand to cool andthereby yielded a stick adhesive.

Example 12

[0285] A water-based silanolated resin composition was prepared by theprocedure of Example 1. In a flask in a thermostatic bath at 80° C., 100parts of the water-based silanolated resin composition (stockcomposition, solid content 40%), 7 parts of sodium stearate, and 5.0parts of the hydrophilic compound (1) were placed with stirring, theresulting mixture was then taken out from the flask 1 hour later, wasplaced in a stick-shaped case without delay, was left stand to cool andthereby yielded a stick adhesive.

Example 13

[0286] A water-based silanolated resin composition was prepared by theprocedure of Example 1. In a flask in a thermostatic bath at 80° C., 100parts of the water-based silanolated resin composition (stockcomposition, solid content 40%), 7 parts of sodium stearate, and 20parts of the hydrophilic compound (1) were placed with stirring, theresulting mixture was then taken out from the flask 1 hour later, wasplaced in a stick-shaped case without delay, was left stand to cool andthereby yielded a stick adhesive.

Example 14

[0287] A water-based silanolated resin composition was prepared by theprocedure of Example 1. In a flask in a thermostatic bath at 80° C., 100parts of the water-based silanolated resin composition (stockcomposition, solid content 40%), 7 parts of sodium stearate, and 5.0parts of the hydrophilic compound (2) were placed with stirring, theresulting mixture was then taken out from the flask 1 hour later, wasplaced in a stick-shaped case without delay, was left stand to cool andthereby yielded a stick adhesive.

Example 15

[0288] A water-based silanolated resin composition was prepared by theprocedure of Example 1. In a flask in a thermostatic bath at 80° C., 100parts of the water-based silanolated resin composition (stockcomposition, solid content 40%), 7 parts of sodium stearate, and 5.0parts of the hydrophilic compound (3) were placed with stirring, theresulting mixture was then taken out from the flask 1 hour later, wasplaced in a stick-shaped case without delay, was left stand to cool andthereby yielded a stick adhesive.

Example 16

[0289] A water-based silanolated resin composition was prepared by theprocedure of Example 1. In a flask in a thermostatic bath at 80° C., 100parts of the water-based silanolated resin composition (stockcomposition, solid content 40%), 7 parts of sodium stearate, and 0.03part of the curing accelerator (1) were placed with stirring, theresulting mixture was then taken out from the flask 1 hour later, wasplaced in a stick-shaped case without delay, was left stand to cool andthereby yielded a stick adhesive.

Example 17

[0290] A water-based silanolated resin composition was prepared by theprocedure of Example 1. In a flask in a thermostatic bath at 80° C., 100parts of the water-based silanolated resin composition (stockcomposition, solid content 40%), 7 parts of sodium stearate, and 0.2part of the curing accelerator (1) were placed with stirring, theresulting mixture was then taken out from the flask 1 hour later, wasplaced in a stick-shaped case without delay, was left stand to cool andthereby yielded a stick adhesive.

Example 18

[0291] A water-based silanolated resin composition was prepared by theprocedure of Example 1. In a flask in a thermostatic bath at 80° C., 100parts of the water-based silanolated resin composition (stockcomposition, solid content 40%), 7 parts of sodium stearate, and 0.03part of the curing accelerator (2) were placed with stirring, theresulting mixture was then taken out from the flask 1 hour later, wasplaced in a stick-shaped case without delay, was left stand to cool andthereby yielded a stick adhesive.

Comparative Example 1

[0292] A stick adhesive was prepared by the procedure of Example 1,except that the amino-group-containing alkoxysilane (A4-a) was not used.Namely, in the stick adhesive according to Comparative Example 1, theends of the polymer serving as an adhesive component are notsilanolated. The composition of the adhesive is shown in Table 2.

Comparative Example 2

[0293] In a flask in a thermostatic bath at 80° C., 100 parts of acommercially available urethane emulsion (trade name: “HYDRAN HW311”available from Dainippon Ink and Chemicals Incorporation) (stockcomposition) and 7 parts of sodium stearate were placed with stirring,the resulting mixture was then taken out from the flask 1 hour later,was placed in a stick-shaped case without delay, was left stand to coolbut failed to yield a stick-shaped product. The composition of thisadhesive is shown in Table 2.

Comparative Example 3

[0294] A commercially available stick adhesive (trade name “SUPERSTICK”available from Konishi Co., Ltd.; main component: polyvinylpyrrolidone)was used as a stick adhesive.

[0295] The properties and proportions of the water-based silanolatedresin compositions according to Examples 1 to 10 are shown in Tables 1and 2. In Tables 1 and 2, the term “NCO/NCO-reactive group (equivalentratio)” means the equivalent ratio (NCO/NCO-reactive group) of anisocyanate group (NCO) in a polyisocyanate compound to anisocyanate-reactive group (NCO-reactive group such as —OH and —NH₂) in acompound containing no anionic group and having pluralisocyanate-reactive groups and a compound having an anionic group andplural isocyanate-reactive groups. The term “Carboxyl group content (%)”means the content (%) of a carboxyl group (COOH) in acarboxyl-group-containing polymer terminally having an alkoxysilylgroup. If the carboxyl group in question is in the form of a salt, it isinterpreted that the carboxyl group is not in the form of a salt. Theterm “Neutralization rate (%)” means the percentage (%) of carboxylgroups that form a salt by neutralization with sodium hydroxide, in thecarboxyl-group-containing polymer terminally having an alkoxysilylgroup. The term “Resin content (%)” means the percentage (%) of awater-based silanolated resin in a water-based silanolated resincomposition. The term “Si content (%)” means the content (%) of siliconatoms (Si) in the water-based silanolated resin. TABLE 1 Example 1 2 3 45 6 Isocyanate-reactive compound 100 100 (A1-a) Isocyanate-reactivecompound 100 (A1-b) Isocyanate-reactive compound 100 100 100 (A1-c)Isocyanate-reactive compound 7.7 7.7 7.7 7.7 6.9 7.7 (A1-d)Isocyanate-reactive compound (A1-e) Isocyanate-reactive compound 16.716.7 16.7 16.7 16.7 16.7 (A2-1) Polyisocyanate (A3-1) 57 57 57 57 57 57Amino-group-containing 9.8 9.8 9.8 19.6 alkoxysilane (A4-a)Amino-group-containing 10.1 alkoxysilane (A4-b) Amino-group-containing6.2 alkoxysilane (A4-c) Amino-group-containing alkoxysilane (A4-3)Amino-group-containing alkoxysilane (A4-4) Amino-group-containingalkoxysilane (A4-5) Sodium hydroxide 4.5 4.5 4.5 4.5 4.5 4.5 Deionizedwater 294 294 294 294 308 288 NCO/NCO-reactive group 1.03 1.03 1.03 1.031.03 1.03 (equivalent ratio) Carboxyl group content (%) 2.6 2.6 2.6 2.62.5 2.6 Neutralization rate (%) 100 100 100 100 100 100 Resin content (%) 40 40 40 40 40 40 Si content (%) 0.24 0.24 0.24 0.24 0.45 0.24 Stockcomposition 100 100 100 100 100 100 Sodium stearate 7 7 7 7 7 7 Stickshape retention Good Good Good Good Good Good Stick slidability GoodGood Good Good Good Good Adhesive strength (N/mm²)hophornbeam/hophornbeam 6.40 6.52 6.44 6.35 5.99 5.89 hophornbeam/ABS4.59 3.76 3.84 4.24 3.41 3.77 hophornbeam/steel plate 4.60 3.34 3.503.59 3.73 3.31 Water resistance Good Good Good Good Good Good Heatresistance Good Good Good Good Good Good Adhesion to glass Good GoodGood Good Good Good Contact property Good Good Good Good Good GoodInitial adhesion — — — — — —

[0296] TABLE 2 Comparative Example Example 7 8 9 10 1 2 3Isocyanate-reactive compound (A1-a) 100 Isocyanate-reactive compound(A1-b) 100 Isocyanate-reactive compound (A1-c) 100 100 100Isocyanate-reactive compound (A1-d) 7.7 7.7 7.7 6.0 7.7Isocyanate-reactive compound (A1-e) 1.6 Isocyanate-reactive compound(A2-1) 16.7 16.7 16.7 16.7 16.7 Polyisocyanate (A3-1) 57 57 57 60.6 57Amino-group-containing alkoxysilane (A4-a) Amino-group-containingalkoxysilane 20.7 (A4-b) Amino-group-containing alkoxysilane (A4-c)Amino-group-containing alkoxysilane 3 (A4-3) Amino-group-containingalkoxysilane 4.3 (A4-4) Amino-group-containing alkoxysilane 3.3 (A4-5)Sodium hydroxide 4.5 4.5 4.5 4.5 4.5 Deionized water 283 285 284 313 279NCO/NCO-reactive group (equivalent 1.03 1.03 1.03 1.07 1.03 ratio)Carboxyl group content (%) 2.7 2.7 2.7 2.4 2.7 Neutralization rate (%)100 100 100 100 100 Resin content (%) 40 40 40 40 40 Si content (%) 0.240.24 0.24 0.47 0 Stock composition 100 100 100 100 100 100 Sodiumstearate 7 7 7 7 7 7 Stick shape retention Good Good Good Good Fair *1Good Stick slidability Good Good Good Good Fair *1 Good Adhesivestrength (N/mm²) hophornbeam/hophornbeam 5.38 5.32 5.22 6.81 3.77 *10.64 hophornbeam/ABS 3.59 3.58 3.63 4.66 2.85 *1 0.16 hophornbeam/steelplate 3.26 3.16 3.19 4.79 2.07 *1 0.21 Water resistance Good Good GoodGood Poor *1 Poor Heat resistance Good Good Good Good Good *1 PoorAdhesion to glass Good Good Good Good Poor *1 Poor Contact propertiesGood Good Good — Poor *1 Very poor Initial adhesion — — — Good — *1 —

[0297] Determination

[0298] The stick shape retention, stick slidability, adhesive strength,water resistance, heat resistance, and adhesion to glass of the stickadhesives according to Examples 1 to 10, Comparative Examples 1 and 3were determined according to the following determination methods. Inaddition, the contact bonding property of the stick adhesives accordingto Examples 1 to 9 and Comparative Examples 1 and 3 and the initialadhesion of the stick adhesive according to Example 10 were determined,respectively, according to the following determination methods. Thus,the stick shape retention, stick slidability, adhesive strength, waterresistance, heat resistance, adhesion to glass, contact bondingproperty, and initial adhesion (fast curing properties) were determined.The results are also shown in Table 1 and 2. The adhesive according toComparative Example 2 could not be formed into a stick, and itsproperties could not be determined.

[0299] [Determination Method for Stick Shape Retention]

[0300] A stick adhesive was applied to a hophornbeam, a broad-leavedtree material, and the shape of the stick adhesive during and after theapplication was visually observed, and the stick shape retention wasrated according to the following criteria. The determined results areshown in the column of “Stick shape retention” in the tables.

[0301] Criteria

[0302] Good: The stick adhesive keeps its original shape withoutdistortion.

[0303] Fair: The stick adhesive becomes distorted to some extent.

[0304] Poor: The stick adhesive is brittle and immediately becomesdistorted.

[0305] [Determination Method for Stick Slidability]

[0306] A stick adhesive was applied to a hophornbeam, a broad-leavedtree material, and ease of application of the stick adhesive was ratedby sensory feeling according to the following criteria. The determinedresults are shown in the column of “Stick slidability” in the tables.

[0307] Criteria

[0308] Excellent: The stick adhesive is very easy to apply.

[0309] Good: The stick adhesive is easy to apply.

[0310] Fair: The stick adhesive is not applied smoothly to some extentand is difficult to apply.

[0311] Poor: The stick adhesive is very difficult to apply or cannot beapplied.

[0312] [Determination Method for Adhesive Strength]

[0313] As adherends, hophornbeam/hophornbeam (each 100 mm×25 mm×5 mm),hophornbeam (100 mm×25 mm×5 mm)/molded plate (100 mm×25 mm×3 mm) made ofan acrylonitrile-butadiene-styrene copolymer (ABS), and hophornbeam (100mm×25 mm×5 mm)/stainless steel plate (100 mm×25 mm×2 mm) were used. Eachthree coats of a stick adhesive were applied to each one surface of thetwo adherends to an amount of about 30 g/m², and the two surfaces wereattached and pressed with manual pressure at a temperature of 23° C. ata humidity of 55% RH. The resulting article was aged at a temperature of23° C. at a humidity of 55% RH for 3 days. The shearing adhesivestrength as the adhesive strength of the article was then determinedaccording to Japanese Industrial Standards (JIS) K 6850 at a tensilespeed of 5 mm/min using an Autograph available from ShimadzuCorporation. The determined results are shown in the column “Adhesivestrength” in the tables. The results on the adherendshophornbeam/hophornbeam are shown in the column ofhophornbeam/hophornbeam”, those on the adherends the hophornbeam/moldedplate made of acrylonitrile-butadiene-styrene copolymer are shown in thecolumn of “hophornbeam/ABS”, and those on the adherendshophornbeam/stainless steel plate are shown in the column of“hophornbeam/steel plate” in the tables.

[0314] [Determination Method for Water Resistance]

[0315] Each three coats of a stick adhesive were applied to one surfaceof two adherends broad-leaved tree materials hophornbeam/hophornbeam(each 100 mm×25 mm×5 mm) to an amount of about 30 g/m², and the twosurfaces were attached and pressed with manual pressure at a temperatureof 23° C. at a humidity of 55% RH. The resulting article was aged at atemperature of 23° C. at a humidity of 55% RH for 3 days and was thenimmersed in water at 23° C. for 1 day. The adhesive strength of theresulting article was determined by a tensile shearing test according toJIS K 6850, and the water resistance of the stick adhesive according tothe following criteria. The results are shown in the column of “Waterresistance” in the tables.

[0316] Criteria

[0317] Excellent: The adhesive strength is 1.0 N/mm² or more.

[0318] Good: The adhesive strength is 0.2 N/mm² or more and less than1.0 N/mm².

[0319] Poor: The adhesive strength is less than 0.2 N/mm².

[0320] [Determination Method for Heat Resistance]

[0321] Each three coats of a stick adhesive were applied to one surfaceof two adherends broad-leaved tree materials hophornbeam/hophornbeam(each 100 mm×25 mm×5mm) to an amount of about 30 g/m², and the twosurfaces were attached and pressed with manual pressure at a temperatureof 23° C. at a humidity of 55% RH. The resulting article was aged at atemperature of 23° C. at a humidity of 55% RH for 3 days and was thenleft at 50° C. for 1 day. The adhesive strength of the resulting articlewas determined by a tensile shearing test according to JIS K 6850, andthe heat resistance of the stick adhesive according to the followingcriteria. The results are shown in the column of “Heat resistance” inthe tables.

[0322] Criteria

[0323] Good: The adhesive strength is 1.0 N/mm² or more.

[0324] Fair: The adhesive strength is 0.2 N/mm² or more and less than1.0 N/mm².

[0325] Poor: The adhesive strength is less than 0.2 N/mm².

[0326] [Determination Method for Adhesion to Glass]

[0327] A stick adhesive was applied to a glass plate, a copy paper wasthen applied thereto and was pressed with manual pressure. The resultingarticle was aged at a temperature of 23° C. at a humidity of 55% RH for1 day. The 180 degree peeling adhesive strength of the resulting articlewas determined at a tensile speed of 200 mm/min using an Autographavailable from Shimadzu Corporation, and the adhesion to glass of thestick adhesive was rated according to the following criteria. Theresults are shown in the column of “Adhesion to glass” in the tables.

[0328] Criteria

[0329] Excellent: The paper is broken.

[0330] Good: The paper is partially broken.

[0331] Poor: The paper is not broken.

[0332] [Determination Method for Contact Bonding Property]

[0333] A coat of a stick adhesive was applied to each one surface of twostainless steel plates (each 100 mm×25 mm×2 mm) as adherends to anamount of about 30 g/m², and the two adherends were attached and pressedby manual pressure after an open time of about 300 seconds at atemperature of 23° C. at a humidity of 55% RH. Immediately thereafter,the shearing adhesive strength as the adhesive strength of the resultingarticle was determined according to JIS K 6850 at a tensile speed of 5mm/min using an Autograph available from Shimadzu Corporation. Thecontact bonding property of the stick adhesive was then rated accordingto the following criteria. The results are shown in the column of“Contact bonding property” in the tables.

[0334] Criteria

[0335] Good: The adhesive strength is 150 mN/mm² or more and theeffective bonding area is 70% or more.

[0336] Poor: The adhesive strength is less than 50 mN/mm² or theeffective bonding area is 10% or more and less than 30%.

[0337] Very poor: The adherends cannot be bonded.

[0338] [Determination Method for Initial Adhesion]

[0339] Each three coats of a stick adhesive were applied to each onesurface of two adherends broad-leaved tree materialhophornbeam/hophornbeam (each 100 mm×25 mm×5 mm) to an amount of about30 g/m², and the two faces were attached and pressed with manualpressure at a temperature of 23° C. at a humidity of 55% RH withoutdelay. The resulting article was aged at a temperature of 23° C. at ahumidity of 55% RH for 3 minutes, and the initial adhesive strength ofthe stick adhesive was determined by a tensile shearing test accordingto JIS K 6850, and the initial adhesion (fast curing property) of thestick adhesive was rated according to the following criteria. Theresults are shown in the column of “Initial adhesion” in the tables.

[0340] Criteria

[0341] Good: The adhesive strength is 1.0 N/mm² or more.

[0342] Poor: The adhesive strength is less than 1.0 N/mm².

[0343] In the criteria in the tests, “Excellent”, “Good”, “Fair”, and“Poor” basically mean “Outstanding”, “Good”, “Average”, and“Unsatisfactory”, respectively.

[0344] The tables show that the stick adhesives of Examples 1 to 10according to the present invention have excellent fitting afterattachment, can easily bond adherends with each other with goodworkability (applying workability). They also have excellent adhesion toplastics, metals, and glass. In addition, the stick adhesives ofExamples 1 to 9 can bond adherends by contact bonding. The stickadhesive of Example 10 has very excellent initial adhesion and can bondadherends immediately after application. The stick adhesives alsoexhibit good water resistance and heat resistance after application.

[0345] The coating performance, spread, bonding reproducibility, andcontact bonding property of the stick adhesives of Examples 11 to 15were determined according to the following determination methods and theaforementioned determination method for contact bonding property. Theresults show that the stick adhesives of Examples 11 to 15 according tothe present invention have excellent coating performance and can besmoothly applied without resistance. They can be easily applied in asatisfactory spread. In particular, the stick adhesives of Examples 12,13 and 15 can be very easily applied in a satisfactory spread withoutunevenness. The stick adhesives also have excellent bondingreproducibility and can effectively exhibit stable adhesivecapabilities. Naturally, they can bond adherends by contact bonding witha long open time (time period within which adherends can be attached)and exhibit excellent contact bonding property.

[0346] The storage stability and adhesive strength development time ofthe stick adhesives of Examples 16 to 18 were determined according tothe following determination methods, and the storage stability and fastcuring property of the stick adhesives were rated. The results show thatthey keep their excellent storage stability and have a short minimumaging time that can allow the adhesives to exhibit an adhesive strengthof 1.0 N/mm² or more and thereby have further improved fast curingproperty.

[0347] In contrast, the stick adhesive according to Comparative Example1 has poor shape retention and slidability, low adhesive strength toadherends, poor water resistance and poor adhesion to glass and cannotbond adherends by contact bonding. The adhesive according to ComparativeExample 2 could not be formed into a stick. The stick adhesive accordingto Comparative Example 3 has good shape retention and slidability buthas poor adhesive strength to adherends, water resistance, heatresistance and adhesion to glass and cannot bond adherends by contactbonding.

[0348] [Determination Method for Coating Performance]

[0349] A stick adhesive was applied to paper by pressing while slidingsideward, and the resistance during this procedure was determined bysensory feeling, and the coating performance was rated. The coatingperformance is rated better with more smooth coating.

[0350] [Determination Method for Spread]

[0351] A stick adhesive was applied to a surface of hophornbeam, abroad-leaved tree material by three reciprocating operation. The coatedamount in this procedure was determined and rated as the spread. Thespread is rated better with an increasing amount.

[0352] [Determination Method for Bonding Reproducibility]

[0353] Each three coats of a stick adhesive were applied to each onemating surface of two adherends broad-leaved tree materialhophornbeam/hophornbeam (each 100 mm×25 mm×5 mm), and the two matingsurfaces were attached and pressed with manual pressure at a temperatureof 23° C. at a humidity of 55% RH without delay and thereby yieldedthree test specimens bonded by the stick adhesive. The test specimenswas aged at a temperature of 23° C. at a humidity of 55% RH for 3 days,and the shearing adhesive strength of the test specimens was determinedaccording to JIS K 6850 at a tensile speed of 5 mm/min using anAutograph available from Shimadzu Corporation. The mean of the adhesivestrength of the three test specimens and the variation from the meanwere determined, and the bonding reproducibility was rated. The bondingreproducibility is rated better with a decreasing variation in the totaltest specimens.

[0354] [Determination Method for Storage Stability]

[0355] The stick shape retention, initial adhesion and spread of a stickadhesive were determined according to the aforementioned determinationmethods before and after storage at 50° C. for 30 days. The storagestability of the stick adhesive after storage at 50° C. for 30 days wasrated with reference to the shape retention, initial adhesion, andspread of the stick adhesive. The storage stability is rated better withless changes in the shape retention, initial adhesion, and spreadbetween before and after storage.

[0356] [Determination Method for Adhesive Strength Development Time]

[0357] Each three coats of a stick adhesive were applied to each onemating surface of two adherends broad-leaved tree materialhophornbeam/hophornbeam (each 100 mm×25 mm×5 mm) to an amount of about30 g/m², and the two mating surfaces were attached and pressed withmanual pressure at a temperature of 23° C. at a humidity of 55% RHwithout delay. The resulting article was aged at a temperature of 23° C.at a humidity of 55% RH for a predetermined time, and the adhesivestrength of the article was determined according to a tensile shearingtest according to JIS K 6850. The aging time (cure time) required toexhibit an adhesive strength of 1.0 N/mm² or more was determined. Thefast curing performance is rated better with a shorter minimum agingtime to exhibit an adhesive strength of 1.0 N/mm² or more.

[0358] Industrial Applicability

[0359] As is described above, the self-curable water-based solidadhesives of the present invention can be applied with good workability(good coating performance), have good fitting after attachment, havegood adhesion to plastics, metals and glass and exhibit excellent heatresistance and water resistance after curing. They are highly safe tohumans and the environment. They also have excellent shape retention andslidability and can be easily applied. In addition, they can bondadherends by contact bonding despite that they are water-based solidadhesives. Accordingly, the self-curable water-based solid adhesives ofthe present invention are very useful as stick adhesives.

1. A self-curable water-based solid adhesive comprising the followingcomponents (A), (B), (C), and (D): (A) an anionic-group-containingpolymer terminally having an alkoxysilyl group, the polymer being areaction product of a compound (A1) containing no anionic group andhaving plural isocyanate-reactive groups, a compound (A2) having ananionic group and plural isocyanate-reactive groups, a polyisocyanatecompound (A3), and-an alkoxysilane compound (A4) containing anisocyanate-reactive group; (B) a basic compound; (C) water; and (D) agelling agent.
 2. The self-curable water-based solid adhesive accordingto claim 1, which is a gelled product of a water-based resin compositionby action of the gelling agent (D), the water-based resin compositioncomprising the anionic-group-containing polymer (A) terminally having analkoxysilyl group, the basic compound (B), and water (C).
 3. Theself-curable water-based solid adhesive according to claim 2, whereinthe anionic group of the anionic-group-containing polymer (A) terminallyhaving an alkoxysilyl group is neutralized by the basic compound (B),and the alkoxysilyl group at the end of the anionic-group-containingpolymer (A) is hydrolyzed by the water (C) in the water-based resincomposition gelled by action of the gelling agent (D).
 4. Theself-curable water-based solid adhesive according to any one of claims 1to 3, wherein the anionic-group-containing polymer (A) terminally havingan alkoxysilyl group is an anionic-group-containing polymer having analkoxy silylated end and being a reaction product of ananionic-group-containing polymer and the alkoxysilane compound (A4)containing an isocyanate-reactive group, the anionic-group-containingpolymer being a reaction product among the compound (A1) containing noanionic group and having plural isocyanate-reactive groups, the compound(A2) having an anionic group and plural isocyanate-reactive groups, andthe polyisocyanate compound (A3).
 5. The self-curable water-based solidadhesive according to anyone of claims 1 to 4, wherein the compound (A1)containing no anionic group and having plural isocyanate-reactive groupscomprises a compound (A1-1) having a number-average molecular weight ofequal to or more than 500, containing no anionic group and having pluralisocyanate-reactive groups, and a compound (A1-2) having anumber-average molecular weight of less than 500, containing no anionicgroup and having plural isocyanate-reactive groups.
 6. The self-curablewater-based solid adhesive according to any one of claims 1 to 5,wherein the anionic group is a carboxyl group.
 7. The self-curablewater-based solid adhesive according to any one of claims 1 to 6,wherein the compound (A2) having an anionic group and pluralisocyanate-reactive groups is a dimethylolalkanoic acid.
 8. Theself-curable water-based solid adhesive according to any one of claims 1to 7, wherein the isocyanate-reactive group of the alkoxysilane compound(A4) is a primary amino group, a secondary amino group, or a mercaptogroup.
 9. The self-curable water-based solid adhesive according to anyone of claims 1 to 8, wherein the alkoxysilane compound (A4) containingan isocyanate-reactive group is an alkoxysilane compound having asecondary amino group and being a reaction product of an alkoxysilanecompound having at least a primary amino group with an unsaturatedcarboxylic ester (A5).
 10. The self-curable water-based solid adhesiveaccording to any one of claims 1 to 9, wherein the alkoxysilane compound(A4) containing an isocyanate-reactive group is an alkoxysilane compoundhaving a secondary amino group and being a reaction product of analkoxysilane compound having a primary amino group and a secondary aminogroup with an unsaturated carboxylic ester (A5).
 11. The self-curablewater-based solid adhesive according to any one of claims 1 to 10,wherein the ratio of the basic compound (B) to the anionic group of theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup is 50% to 120% by mole.
 12. The self-curable water-based solidadhesive according to any one of claims 1 to 11, wherein the ratio ofthe polyisocyanate compound (A3) to the compound (A1) containing noanionic group and having plural isocyanate-reactive groups and thecompound (A2) having an anionic group and plural isocyanate-reactivegroups is such that the equivalent ratio [NCO/NCO-reactive group] of theisocyanate group in the polyisocyanate compound (A3) to the isocyanatereactive groups in the compound (A1) and the compound (A2) is more than1 and less than or equal to 1.5.
 13. The self-curable water-based solidadhesive according to any one of claims 1 to 12, wherein the content ofthe anionic group in the anionic-group-containing polymer (A) terminallyhaving an alkoxysilyl group is 0.2% to 5.0% by mass.
 14. Theself-curable water-based solid adhesive according to any one of claims 1to 13, wherein the content of silicon atom in theanionic-group-containing polymer (A) terminally having an alkoxysilylgroup is 0.05% to 1% by mass.
 15. The self-curable water-based solidadhesive according to any one of claims 1 to 14, further comprising apolyoxyalkylene compound (E) having an unsaturated-bond-containingorganic group and at least an oxyethylene unit.
 16. The self-curablewater-based solid adhesive according to claim 15, wherein thepolyoxyalkylene compound (E) is a polyoxyalkylene compound having anunsaturated-bond-containing group at its end corresponding to apolyoxyalkylene glycol having at least a polyoxyethylene unit exceptwith one of aryl groups, cycloalkenyl groups, cycloalkadienyl groups,and vinyl group introduced into at least one of its ends.
 17. Theself-curable water-based solid adhesive according to one of claims 15and 16, wherein the polyoxyalkylene compound (E) has a number-averagemolecular weight of 100 to
 5000. 18. The self-curable water-based solidadhesive according to any one of claims 15 to 17, wherein the proportionof the polyoxyalkylene compound (E) is 0.1 to 50 parts by mass to 100parts by mass of the anionic-group-containing polymer (A) terminallyhaving an alkoxysilyl group.
 19. The self-curable water-based solidadhesive according to any one of claims 1 to 18, further comprising acuring accelerator (F) represented by following Formula (1):

wherein M is one of tin atom, titanium atom, zirconium atom and bismuthatom; R¹ and R² are the same or different and are each a hydrocarbongroup; R³ and R⁴ are the same or different and are each a hydrogen atomor a hydrocarbon group; R⁵ and R⁶ are the same or different and are eacha hydrogen atom or a hydrocarbon group; p is an integer equal to or morethan 1; and q is an integer from 1 to
 3. 20. A bonding method comprisingthe step of performing contact bonding using the self-curablewater-based solid adhesive according to any one of claims 1 to
 19. 21.An anionic-group-containing polymer represented by following Formula (2)having an alkoxysilyl group at its end, a salt thereof, or a hydrolyzedpolymer being derived from the polymer or the salt thereof andcomprising a hydrolyzed alkoxysilyl group: WNH—CO—X)_(n)   (2) whereinW is a residue corresponding to a skeleton of ananionic-group-containing polymer; the nitrogen atom-combined with W is anitrogen atom derived from an isocyanate group at the end of theanionic-group-containing polymer; W has a structural unit represented byfollowing Formula (2a): NH—CO—V—Y—V—CO—NH-Z  (b 2a) wherein Y is oneof a residue derived from a compound (A1) containing no anionic groupand having plural isocyanate-reactive groups and a residue derived froma compound (A2) having an anionic group and plural isocyanate-reactivegroups; V combined with Y is a group derived from one of theisocyanate-reactive groups of the compound (A1) and the compound (A2),wherein both the residue derived from the compound (A1) and the residuederived from the compound (A2) as Y are contained in the polymer; Z is aresidue derived from a polyisocyanate compound (A3), wherein a nitrogenatom combined with Z and a nitrogen atom on the opposite side to Z arenitrogen atoms derived from isocyanate groups of the polyisocyanatecompound (A3); X is an alkoxysilyl-containing group represented by anyone of following Formulae (2b), (2c), and (2d):

wherein R⁷ and R⁸ are the same or different and are each an alkyl group;R9 is an alkylene group; R¹⁰ and R¹²are the same or different and areeach a hydrogen atom or an alkyl group; R^(11a) is a hydrogen atom or analkyl group; R¹³ is an alkyl group, an aryl group, or a cycloalkylgroup; and m is an integer from 1 to 3:

wherein R⁷ and R⁸ are the same or different and are each an alkyl group;R⁹ and R¹⁴ are the same or different and are each an alkylene group; R¹⁰and R¹² are the same or different and are each a hydrogen atom or analkyl group; R¹¹ is a hydrogen atom, an alkyl group, an aryl group, analkoxycarbonyl group, an aryloxycarbonyl group, or acycloalkyloxycarbonyl group; R¹³ is an alkyl group, an aryl group, or acycloalkyl group; and m is an integer from 1 to 3:

wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, and m have the samemeanings as defined above; and n is an integer from 1 to
 4. 22. Theanionic-group-containing polymer terminally having an alkoxysilyl group,the salt thereof, or the hydrolyzed polymer according to claim 21,wherein, in Formula (2a), Y is one of a residue derived from a polyolcompound (A1) containing no anionic group and a residue derived from apolyol compound (A2) containing an anionic group; and V combined with Yis an oxygen atom derived from one of a hydroxy group of the polyolcompound (A1) and a hydroxyl group of the polyol compound (A2), whereinboth the residue derived from the polyol compound (A1) and the residuederived from the polyol compound (A2) are contained in the polymer. 23.The anionic-group-containing polymer terminally having an alkoxysilylgroup, the salt thereof, or the hydrolyzed polymer according to claim22, wherein, in Formula (2a), Y is one of a residue derived from apolyol compound (A1-1) containing no anionic group and having anumber-average molecular weight of equal to or more than 500, a residuederived from a polyol compound (A1-2) containing no anionic group andhaving a number-average molecular weight of less than 500, and a residuederived from the polyol compound (A2) containing an anionic group; and Vcombined with Y is an oxygen atom derived from one of a hydroxy group ofthe polyol compound (A1-1), a hydroxyl group of the polyol compound(A1-2), and a hydroxyl group of the polyol compound (A2), and whereinall the residue derived from the polyol compound (A1-1), the residuederived from the polyol compound (A1-2), and the residue derived fromthe polyol compound (A2) are contained in the polymer.
 24. Theanionic-group-containing polymer terminally having an alkoxysilyl group,the salt thereof, or the hydrolyzed polymer according to claim 23,wherein the anionic-group-containing polymer represented by Formula (2)terminally having an alkoxysilyl group is an anionic-group-containingpolymer having an alkoxysilylated end and being a reaction product of:an anionic-group-containing polymer, the anionic-group-containingpolymer being a reaction product of: the polyol compound (A1-1)containing no anionic group and having a number-average molecular weightof equal to or more than 500; the polyol compound (A1-2) containing noanionic group and having a number-average molecular weight of less than500; the polyol compound (A2) containing an anionic group; and thepolyisocyanate compound (A3), and at least onesecondary-amino-group-containing alkoxysilane compound selected fromalkoxysilane compounds each having one secondary amino group representedby one of following Formulae (3a), (3b), and (3c):

wherein R⁷, R⁸, R⁹, R¹⁰, R^(11a), R¹², R¹³, and m have the same meaningsas defined above;

wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, and m have the samemeanings as defined above;

wherein R⁷, R⁸, R⁹, R¹⁰, R¹¹, R¹², R¹³, R¹⁴, and m have the samemeanings as defined above.